Global variation of the para hydrogen fraction in Jupiter's atmosphere and implications for dynamics on the outer planets

Infrared spectra obtained by the Voyager spacecraft indicate that the para hydrogen fraction near the 300-mbar pressure level on Jupiter is not in thermodynamic equilibrium. Analysis of the global mapping data sequences from Voyagers 1 and 2 shows that the para fraction is smallest at equatorial latitudes, and approaches equilibrium at high latitudes. The sampled atmospheric level is near 125°K and the equatorial para fraction would represent thermal equilibrium at about 160°K. There are small-scale variations superposed on the global pattern, and these do not correlate with albedo, flow velocity, or 5-μm brightness.Lack of correlation of cloud indicators with the para fraction suggests that catalysis of ortho-para conversion does not occur on aerosol surfaces, at least near the 300 mbar level. The fact that dynamics alters the para fraction from equilibrium while not affecting temperatures to a large degree suggests that the para hydrogen equilibration rate is slower than radiative thermal adjustment. A survey of the mechanisms for equilibration suggests that H₂H₂ paramagnetic interaction is dominant. The slow equilibration rate has dynamical implications for all the outer planets. A mixing length model is used to demonstrate that within the convective lower tropospheres of the giant planets there is very slow overturning. The mean structures are close to equilibrium para fraction, the thermal structures are equilibrium adiabats, and they are statically stable to high frequency dynamical perturbations. The para hydrogen conversion greatly increases the efficiency of convection. Within Jupiter's stably stratified upper troposphere, where the infrared spectra originate, the global variation of the para fraction appears most likely to be produced by upwelling at equatorial latitudes in response to solar heating. If this is true, there is compensating downward motion in polar regions.     

Ionization freeze-out and hydrogen excitation in the SN IIP atmosphere

We study the nonstationary recombination of hydrogen in the atmosphere of SN 1987A by taking into account ion-molecular processes. The hydrogen excitation due to nonstationary recombination is shown to be enough to explain the observed hydrogen lines in a time interval until day 30 in the absence of additional excitation mechanisms. Thus, the problem of a deficit in the hydrogen excitation that has recently been found in modeling the hydrogen spectrum of SN 1987A at an early photospheric stage by assuming statistical ionization equilibrium is resolved. The mass of the radioactive ⁵⁶Ni with a spherically symmetric distribution in the outer layers is shown to be close to 10^?6 M _⊙. Our model predicts the appearance of a blue peak in the Hα profile between days 20 and 30. This peak bears a close similarity to the observed peak known as the Bochum event. The presence of this peak in the model is attributable to nonstationary recombination and to a substantial contribution of hydrogen neutralization involving H^? and H₂.     

Venus: Preliminary prediction of the mineral composition of surface rocks

A thermodynamical analysis of the multicomponent system SiTiAlFeMnMgCaNaKPCHO open with respect to CO₂, CO, H₂O was carried out. Hydration and carbonatization processes are proposed to be geochemical consequences of the hypothesis of quasi-equilibrium conditions between the troposphere and crustal surface rocks. The probable rock-forming hydrated mineral phases are represented by epidote, glaucophane, tremolite, phlogopite, and annite; the carbonatization results in existence of calcite and dolomite as rock-forming minerals of weathered alkaline lavas. The surface rocks are assumed to have high ferric/ferrous iron ratios. The wollastonite equilibrium is rejected as a buffering chemical reaction. Hydrated minerals could be stable at least up to 5-km depths and contribute about 0.1 × 10²⁴ g of H₂O whereas about (0.7–0.8) × 10²⁴ g of H₂O would be consumed in ferrous iron oxidation with concomitant hydrogen dissipation. The distribution of H₂O in the outer planetary shells is possibly a function of their temperatures.     

Transient conditions for biogenesis on low-mass exoplanets with escaping hydrogen atmospheres

Exoplanets with lower equilibrium temperatures than Earth and primordial hydrogen atmospheres that evaporate after formation should pass through transient periods where oceans can form on their surfaces, as liquid water can form below a few thousand bar pressure and H₂–H₂ collision-induced absorption provides significant greenhouse warming. The duration of the transient period depends on the planet size, starting H₂ inventory and star type, with the longest periods typically occurring for planets around M-class stars. As pre-biotic compounds readily form in the reducing chemistry of hydrogen-rich atmospheres, conditions on these planets could be favourable to the emergence of life. The ultimate fate of any emergent organisms under such conditions would depend on their ability to adapt to (or modify) their gradually cooling environment.     

The aeronomy of the upper atmosphere of Venus

Density profiles for CO, O, and O₂ in the Cytherean atmosphere above 90 km are plotted with eddy diffusion coefficient (K) as a parameter, subject to the constraint that the mixing ratios of CO and O₂ approach their observed value or values under the observed upper limit at the lower boundary. It is then shown that the value of K puts upper limits on the amount of hydrogen (in the form of H₂O, HCl, and H₂) the atmosphere near 90km can contain. This value is a function of the density and temperature of hydrogen at the critical level and the magnitude of the total escape flux, where unspecified flux mechanisms other than thermal are postulated ad hoc. In general these constraints call for large values of K to accomodate the atomic hydrogen produced by measured mixing ratios of HCl and H₂O. Hence they constrain thee amount of O in the upper atmosphere to values well under 1% at 130 km unless there are very large hydrogen escape fluxes, 10⁷ cm^?2sec^?1 or larger. The freedom to assume arbitrary amounts of H₂ in the atmosphere is also restricted. We suggest either very effective escape mechanisms—despite low exospheric hydrogen densities—or novel excitation mechanisms for O(3³S) and O(3⁵S) in the upper atmosphere.     

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.     

Mechanisms for incorporation of hydrogen in and on terrestrial planetary surfaces

Storage of hydrogen atoms in or on a planetary surface can take place via several different mechanisms. If the hydrogen atom reacts to form a hydroxyl (OH) group or water molecule, an absorption band near 3 μm will be present. Many possible mechanisms for sequestering atomic hydrogen are discussed: internal hydrogen in the form of non-structural OH and H₂O in nominally-anhydrous minerals, structural OH in minerals, structural H₂O in minerals, H₂O in fluid inclusions, and OH and H₂O in glasses; bulk H₂O as either liquid water or ice; and surficial hydrogen that is either physisorbed as H₂O, chemisorbed as an H₂O surface complex, or chemically-bound as an OH group on surface terminal sites and grain boundary regions. Understanding the spectroscopic distinctions among these various phenomena is of critical importance in constraining both the evolution of planetary interiors and the cycling of water on planetary surfaces. Proper interpretation of 3-μm bands in reflectance spectra is shown to depend upon the relative contributions from surficial vs. interior hydrogen, which vary with effective surface area (i.e., the grain size and surface roughness) and the volume sampled by the spectrometer.     

The role of submicrometer aerosols and macromolecules in H2 formation in the titan haze

Previous studies of the photochemistry of small molecules in Titan’s atmosphere found it difficult to have hydrogen atoms removed at a rate sufficient to explain the observed abundance of unsaturated hydrocarbons. One qualitative explanation of the discrepancy nominated catalytic aerosol surface chemistry as an efficient sink of hydrogen atoms, although no quantitative study of this mechanism was attempted. In this paper, we quantify how haze aerosols and macromolecules may efficiently catalyze the formation of hydrogen atoms into H₂. We describe the prompt reaction model for the formation of H₂ on aerosol surfaces and compare this with the catalytic formation of H₂ using negatively charged hydrogenated aromatic macromolecules. We conclude that the PRM is an efficient mechanism for the removal of hydrogen atoms from the atmosphere to form H₂ with a peak formation rate of ∼ 70 cm⁻³ s⁻¹ at 420 km. We also conclude that catalytic H₂ formation via hydrogenated anionic macromolecules is viable but much less productive (a maximum of ∼ 0.1 cm⁻³ s⁻¹ at 210 km) than microphysical aerosols.     

Two-dimensional distributions of physical parameters in the prominence of 1984 March 23

The spectral lines Hα Hβ and CaII K of a quiescent prominence are studied using the completely linearized model. The physical parameters (T_e, v_t, N_H) at several locations are obtained. Itis shown: (1) Near the axis of the prominence, kinetic temperature and hydrogen density decrease, while microturbulent velocity increases, with increasing height. (2) Near the edge, the kinetic temperature does not vary with height; but it increases from the center to the edge. (3) Hydrostatic equilibrium does not hold in prominences, and magnetic field plays an important role in supporting them.     

On the rotational energy distributions of reactive, non-polar species in the interstellar medium

A basic model for the formation of non-equilibrium rotational energy distributions is described for reactive, homo-polar diatomic molecules and ions in the interstellar medium. Kinetic models were constructed to calculate the rotational populations of $\mathrm{C}_{2}^{+}$ under the conditions it would experience in the diffuse interstellar medium. As the non-polar ion reacts with molecular hydrogen, but not atomic hydrogen, the thermalization of a hot nascent rotational population will be arrested by chemical reaction when the H₂ density begins to be significant. Populations that deviate strongly from the local thermodynamic equilibrium are predicted for $\mathrm{C}_{2}^{+}$ in environments where it may be detectable. Consequences of this are discussed and a new optical spectrum is calculated.     

The hydrogen ortho-to-para ratio in the stratospheres of the giant planets

Observations of the H₂ S(0) and S(1) quadrupole lines in the four giant planets by the short-wavelength spectrometer of the Infrared Space Observatory are analyzed. These lines probe pressure levels located between 10 and 1 mbar and allow us to determine the stratospheric hydrogen para fraction for the first time. In Jupiter and Saturn, the stratospheric para fraction is close to its tropopause value. In the stratosphere of these planets as well as in Neptune’s, the para fraction presents a significant departure from thermodynamic equilibrium. This situation results from a lagged conversion between the ortho and the para states as molecular hydrogen is transported upward under the influence of turbulent eddy diffusion. In contrast, the uranian stratosphere lies close to thermodynamic equilibrium. The magnitude of the departure from thermodynamic equilibrium appears to be anti-correlated with the amount of stratospheric aerosols. To validate this assumption, we estimate the hydrogen equilibration time with a one-dimensional diffusion model for different conversion processes in the gas phase or on aerosols. The comparison between our results and the tropospheric estimates from Conrath et al. (1998, Icarus,135, 501-517) shows that paramagnetic conversion on aerosols matches the estimated tropospheric and stratospheric relaxation times in the four giant planets. In contrast, paramagnetic conversion in the gas phase can only explain the relaxation times measured in Jupiter and Saturn atmospheres. This situation provides quantitative evidence for an equilibration mechanism dominated by conversion on aerosols.     

Possibilities for the detection of hydrogen peroxide-water-based life on Mars by the Phoenix Lander

The Phoenix Lander landed on Mars on 25 May 2008. It has instruments on board to explore the geology and climate of subpolar Mars and to explore if life ever arose on Mars. Although the Phoenix mission is not a life detection mission per se, it will look for the presence of organic compounds and other evidence to support or discredit the notion of past or present life.The possibility of extant life on Mars has been raised by a reinterpretation of the Viking biology experiments [Houtkooper, J. M., Schulze-Makuch, D., 2007. A possible biogenic origin for hydrogen peroxide on Mars: the Viking results reinterpreted. International Journal of Astrobiology 6, 147-152]. The results of these experiments are in accordance with life based on a mixture of water and hydrogen peroxide instead of water. The near-surface conditions on Mars would give an evolutionary advantage to organisms employing a mixture of H₂O₂ and H₂O in their intracellular fluid: the mixture has a low freezing point, is hygroscopic and provides a source of oxygen. The H₂O₂-H₂O hypothesis also explains the Viking results in a logically consistent way. With regard to its compatibility with cellular contents, H₂O₂ is used for a variety of purposes in terran biochemistry. The ability of the anticipated organisms to withstand low temperatures and the relatively high water vapor content of the atmosphere in the Martian arctic, means that Phoenix will land in an area not inimical to H₂O₂-H₂O-based life. Phoenix has a suite of instruments which may be able to detect the signatures of such putative organisms.     

Synthesis of hydrogen peroxide in water ice by ion irradiation

We present infrared absorption studies on the effects of 50-100 keV Ar⁺ and 100 keV H⁺ ion irradiation of water ice films at 20-120 K. The results support the view that energetic ions can produce hydrogen peroxide on the surface of icy satellites and rings in the outer Solar System, and on ice mantles on interstellar grains. The ion energies are characteristic of magnetospheric ions at Jupiter, and therefore the results support the idea that radiolysis by ion impact is the source of the H₂O₂ detected on Europa by the Galileo infrared spectrometer. We found that Ar⁺ ions, used to mimic S⁺ impacts, are roughly as efficient as H⁺ ions in producing H₂O₂, and that 100 keV H⁺ ions can produce hydrogen peroxide at 120 K. The synthesized hydrogen peroxide remained stable while warming the ice film after irradiation; the column density of the formed H₂O₂ is constant until the ice film begins to desorb, but the concentration of H₂O₂ increases with time during desorption because the water sublimes at a faster rate. Comparing the shape of the 3.5-μm absorption feature of H₂O₂ to the one measured on Europa shows excellent agreement in both shape and position, further indicating that the H₂O₂ detected on Europa is likely caused by radiolysis of water ice.     

Equilibrium constants of the molecular ion H 3 +

Thd H ₃ ⁺ molecular ion plays an important role in the chemistry of astronomical objects as it protonates the neutral species. The authors have recently calculated the partition functions of H ₃ ⁺ which may be used to compute the equilibrium constants for the chemical reaction H₂+H₂ ⁺H ₃ ⁺ +H. In this short communication we have calculated the equilibrium constants for the temperature range from 500 to 8000 K. The results are also presented in the polynomial form.     

HST NICMOS and WFPC2 observations of molecular hydrogen and dust in the central galaxies in cluster cooling flows

We present preliminary results of HST imaging observations of three central galaxies in X-ray luminous clusters of galaxies with putative major cooling flows in their cores: NGC 1275 in the Perseus cluster, Abell 2597, and PKS 0745-19. Narrow-band NICMOS imaging at 2 microns reveals extended, warm (T∼2000–3000 K) molecular hydrogen structures in the cores of Abell 2597 and PKS 0745-19 that appear to be co-spatial with the ionized hydrogen revealed in Hα+[N II] images obtained with WFPC2. The H₂/Hα emission line ratio is unexpectedly high in Abell 2597 and PKS 0745-191: too high to be explained by shocks with v>50 km s⁻¹ or by power-law photo-ionization. Photo-ionization by the surrounding X-ray gas is unlikely in Abell 2597. Fluorescent heating by hot stars is plausible in both Abell 2597 and PKS 0745-191. No extended H₂ emission was discovered in NGC 1275. The H₂/H_α ratio allowed by our detection limits are consistent with shocks or nuclear photo-ionization in NGC 1275. A paper by Donahue et al. is in preparation.     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

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

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

The influence of grain mantles on the formation of hydrogen molecules on grain surfaces

The physical adsorption energy,E, of hydrogen molecules on various substrates at temperatures between 5 and 30 K and at the lowest practicable gas densities has been measured. Values ofE/k are for condensed CO 340 K, CO₂ 800 K, H₂O 850 K and for ‘dirty’ graphite 980 K and ‘dirty’ copper 800 K. From these measurements temperature ranges in which H atoms might combine on the surface to form H₂ molecules are estimated. Duley has discussed the formation and composition of condensed gas mantles on interstellar grains. The effects of such mantles in promoting and poisoning hydrogen molecule formation are discussed.     

On the detectability of H2S in Jupiter

The influence of hydrogen sulfide, a still-undetected key molecule for the Jovian atmospheric chemistry in the infrared spectrum, was investigated. Synthetic spectra including various vertical distribution profiles of H₂S have been computed and compared with observational data for Jupiter in the 2- to 15-cm^?1 and 1160- to 1200-cm^?1 spectral ranges. No firm conclusion about the presence of H₂S can be drawn from the latter spectral region because of large uncertainties in gaseous opacities. In the microwave range, H₂S is found to be a possible candidate to explain the measurements. Constraints to its vertical distribution which would imply a significant supersaturation in the troposphere are derived. Physical and chemical processes involving H₂S in the atmosphere are discussed in the light of this hypothesis.     

Suprathermal hydrogen produced by the dissociation of molecular hydrogen in the extended atmosphere of exoplanet HD 209458b

The ionization and dissociation of molecular hydrogen by the ultraviolet (UV) radiation of the parent star lead to the formation of hydrogen atoms with an excess of kinetic energy and, thus, are an important source of suprathermal hydrogen atoms in the upper atmosphere of exoplanet HD 209458b. Contemporary aeronomical models did not investigate these processes because they assumed the fast local thermalization of the hot atoms of hydrogen by elastic collisions. However, the kinetics and transfer of these atoms were not calculated in detail, because they require the solving of the Boltzmann equation for a nonthermal atom population. This work estimates the effect of the UV radiation of the parent star and the accompanying photocleacton flux on the production of the suprathermal fraction of atomic hydrogen in the H₂ → H transition region. We also consider the formation of the escaping flux of Hatoms created by this effect in the upper atmosphere of HD 209458b. We calculate the production rate and energy spectrum of the hydrogen atoms with excess kinetic energy during the dissociation of H₂. Using the numerical stochastic model created by Shematovich (2004) for a hot planetary corona, we investigate the molecular-scale kinetics and transfer of suprathermal hydrogen atoms in the upper atmosphere and the emergent flux of atoms evaporating from the atmosphere. The latter is estimated as 3.4 × 10¹² cm⁻² s⁻¹ for a moderate stellar activity level of UV radiation, which leads to a planetary atmosphere evaporation rate of 3.4 × 10⁹ g s⁻¹ due to the process of the dissociation of H₂. This estimate is close to the observational value of ∼10¹⁰ g s⁻¹ for the rate of atmospheric loss of HD 209458b.