Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

We investigate the chemical transition of simple molecules like C₂H₂ and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help illuminate and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, which will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics, polymers of HCN and other nitriles, and polyynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C₂H₂, HCN, HC₃N and other nitriles, and C₆H₆) from the gas phase to the haze. We use a one-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursor macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4×10⁻¹⁴ g cm⁻² s⁻¹ and a C/N?4. These results are compared with experimental data, and to microphysical model requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, which will be a great challenge for our understanding of these chemical processes.     

Atomic and molecular hydrogen budget in Titan’s atmosphere

Using a one-dimensional model, we investigate the hydrogen budget and escape to space in Titan’s atmosphere. Our goal is to study in detail the distributions and fluxes of atomic and molecular hydrogen in the model, while identifying sources of qualitative and quantitative uncertainties. Our study confirms that the escape of atomic and molecular hydrogen to space is limited by the diffusion through the homopause level. The H distribution and flux inside the atmosphere are very sensitive to the eddy diffusion coefficient used above altitude 600 km. We chose a high value of this coefficient 1 × 10⁸ cm² s⁻¹ and a homopause level around altitude 900 km. We find that H flows down significantly from the production region above 500 km to the region [300-500] km, where it recombines into H₂. Production of both H and H₂ also occurs in the stratosphere, mostly from photodissociation of acetylene. The only available observational data to be compared are the escape rate of H deduced from Pioneer 11 and IUE observations of the H torus 1-3 × 10⁹ cm⁻² s⁻¹ and the latest retrieved value of the H₂ mole fraction in the stratosphere: (1.1 ± 0.1) × 10⁻³. Our results for both of these values are at least 50-100% higher, though the uncertainties within the chemical schemes and other aspects of the model are large. The chemical conversion from H to H₂ is essentially done through catalytic cycles using acetylene and diacetylene. We have studied the role of this diacetylene cycle, for which the associated reaction rates are poorly known. We find that it mostly affects C₄ species and benzene in the lower atmosphere, rather than the H profile and the hydrogen budget. We have introduced the heterogenous recombination of hydrogen on the surface of aerosol particles in the stratosphere, and this appears to be a significant process, comparable to the chemical processes. It has a major influence on the H distribution, and consequently on several other species, especially C₃H₄, C₄H₂ and C₆H₆. Therefore, this heterogenous process should be taken into account when trying to understand the stratospheric distribution of these hydrocarbons.     

Molecular hydrogen in Titan’s atmosphere: Implications of the measured tropospheric and thermospheric mole fractions

The third most abundant species in Titan’s atmosphere is molecular hydrogen with a tropospheric/lower stratospheric mole fraction of 0.001 derived from Voyager and Cassini infrared measurements. The globally averaged thermospheric H₂ mole fraction profile from the Cassini Ion Neutral Mass Spectrometer (INMS) measurements implies a small positive gradient in the H₂ mixing ratio from the tropopause region to the lower thermosphere (∼950-1000 km), which drives a downward H₂ flux into Titan’s surface comparable to the H₂ escape flux out of the atmosphere (∼2 × 10¹⁰ cm⁻² s⁻¹ referenced to the surface) and requires larger photochemical production rates of H₂ than obtained by previous photochemical models. From detailed model calculations based on known photochemistry with eddy, molecular, and thermal diffusion, the tropospheric and thermospheric H₂ mole fractions are incompatible by a factor of ∼2. The measurements imply that the downward H₂ surface flux is in substantial excess of the speculative threshold value for methanogenic life consumption of H₂ (McKay, C.P., Smith, H.D. [2005], Icarus 178, 274-276. doi:10.1016/j.icarus.2005.05.018), but without the extreme reduction in the surface H₂ mixing ratio.     

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.     

Cassini CIRS update on stratospheric ices at Titan's winter pole

A strong, broad spectral emission feature at 85° N latitude centered at 221 cm⁻¹ remains unidentified after candidate ices of H₂O and pure crystalline CH₃CH₂CN are unambiguously ruled out. A much shallower weak emission feature starts at 160 cm⁻¹ and blends into the strong feature at ∼190 cm⁻¹. This feature is consistent with one formed by an HCN ice cloud composed of ?5 μm radius particles that resides in the lower stratosphere somewhere below an altitude of 160 km. Titan's stratospheric aerosol appears to have a spectral emission feature at about 148 cm⁻¹. The aerosol abundance at 85° N is about a factor 2.2 greater than at 55° S.     

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

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

Titan's aerosols: Comparison between our model and DISR findings

Our model [Dimitrov, V., Bar-Nun, A., 1999. A model of energy dependent agglomeration of hydrocarbon aerosol particles and implication to Titan's aerosol. J. Aerosol. Sci. 30(1), 35-49] describes the experimentally found polymerization of C₂H₂ and HCN to form aerosol embryos, their growth and adherence to form various aerosols objects [Bar-Nun, A., Kleinfeld, I., Ganor, E., 1988. Shape and optical properties of aerosols formed by photolysis of C₂H₂, C₂H₄ and HCN. J. Geophys. Res. 93, 8383-8387]. These loose fractal objects describe well the findings of DISR on the Huygens probe [Tomasko, M.G., Bézard, B., Doose, L., Engel, S., Karkoschka, E., 2008. Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere. Planet. Space Sci., this issue, doi:10.1016/j.pss.2007]. These include (1) various regular objects of R=(0.035-0.064)×10⁻⁶ m, as compared with DISR's 0.05×10⁻⁶ m; (2) diverse low and high fractal structures composed of random combinations of various regular and irregular objects; (3) the number density of fractal particles is 6.9×10⁶ m⁻³ at Z=100 km, as compared with DISR's finding of 5.0×10⁶ m⁻³ at Z=80 km; (4) the number of structural units per higher fractals in the atmosphere at Z∼100 km is (2400-2700), as compared with DISR's 3000, and their size being of R=(5.4-6.4)×10⁻⁶ m will satisfy this value and (5) condensation of CH₄ on the highly fractal structures could begin at the altitude where thin methane clouds were observed, filling somewhat the new open fractal structures.     

Ozone and photochemistry of the Martian lower atmosphere

The calculation of number densities of CO₂, H₂O and N₂ photolysis products was carried out for the Martian atmosphere at heights up to 60 km. The ozone distributed in the atmosphere as a layer of 10 km width with [O₃] max = 2.5 × 10⁹ cm³ at height of 35 km which agree well with the results of u.v. observations on the evening terminator from the Mars-5 satellite. The calculated densities of O₂, CO and H₂O are also in good agreement with the measured data. The eddy diffusion coefficient is equal to 3 × 10⁶ in the troposphere (h ? 30 km) and 10⁸ cm² s^?1 above 40 km. The dependence of the total ozone content on water vapour amount in the atmosphere is considered; the hypothesis about the influence of water ice aerosol on the ozone formation is proposed to explain the high concentrations of ozone in the morning.     

Negative ion chemistry in Titan's upper atmosphere

The Electron Spectrometer (ELS), one of the sensors making up the Cassini Plasma Spectrometer (CAPS) revealed the existence of numerous negative ions in Titan's upper atmosphere. The observations at closest approach (∼1000 km) show evidence for negatively charged ions up to ∼10,000 amu/q, as well as two distinct peaks at 22±4 and 44±8 amu/q, and maybe a third one at 82±14 amu/q. We present the first ionospheric model of Titan including negative ion chemistry. We find that dissociative electron attachment to neutral molecules (mostly HCN) initiates the formation of negative ions. The negative charge is then transferred to more acidic molecules such as HC₃N, HC₅N or C₄H₂. Loss occurs through associative detachment with radicals (H and CH₃). We attribute the three low mass peaks observed by ELS to CN⁻, C₃N⁻/C₄H⁻ and C₅N⁻. These species are the first intermediates in the formation of the even larger negative ions observed by ELS, which are most likely the precursors to the aerosols observed at lower altitudes.     

Vertical profile of H2SO4 vapor at 70-110 km on Venus and some related problems

The vertical profile of H₂SO₄ vapor is calculated using current atmospheric and thermodynamic data. The atmospheric data include the H₂O profiles observed at 70-112 km by the SOIR solar occultations, the SPICAV-UV profiles of the haze extinction at 220 nm, the VeRa temperature profiles, and a typical profile of eddy diffusion. The thermodynamic data are the saturated vapor pressures of H₂O and H₂SO₄ and chemical potentials of these species in sulfuric acid solutions. The calculated concentration of sulfuric acid in the cloud droplets varies from 85% at 70 km to a minimum of 70% at 90 km and then gradually increasing to 90-100% at 110 km. The H₂SO₄ vapor mixing ratio is ∼10⁻¹² at 70 and 110 km with a deep minimum of 3 × 10⁻¹⁸ at 88 km. The H₂O-H₂SO₄ system matches the local thermodynamic equilibrium conditions up to 87 km. The column photolysis rate of H₂SO₄ is 1.6 × 10⁵ cm⁻² s⁻¹ at 70 km and 23 cm⁻² s⁻¹ at 90 km. The calculated abundance of H₂SO₄ vapor at 90-110 km and its photolysis rate are smaller than those presented in the recent model by Zhang et al. (Zhang, X., Liang, M.C., Montmessin, F., Bertaux, J.L., Parkinson, C., Yung, Y.L. [2010]. Nat. Geosci. 3, 834-837) by factors of 10⁶ and 10⁹, respectively. Assumptions of 100% sulfuric acid, local thermodynamic equilibrium, too warm atmosphere, supersaturation of H₂SO₄ (impossible for a source of SO_X), and cross sections for H₂SO₄·H₂O (impossible above the pure H₂SO₄) are the main reasons of this huge difference. Significant differences and contradictions between the SPICAV-UV, SOIR, and ground-based submillimeter observations of SO_X at 70-110 km are briefly discussed and some weaknesses are outlined. The possible source of high altitude SO_X on Venus remains unclear and probably does not exist.     

The Unusual Absorption Line Spectrum of Quasar SDSS J2220+0109

We report the Balmer broad absorption lines (BALs) in the quasar SDSS J2220 + 0109 discovered from the SDSS data, and present a detailed analysis of the peculiar absorption line spectrum, including the He I* multiplet at λλ3189, 3889 arising from the metastable 2³s-state helium and the Balmer Hα and Hβ lines from the excited hydrogen H I of n = 2 level, which are rarely seen in quasar spectra, as well as many absorption lines arising from the excited Fe II* of the levels 7 955 cm⁻¹, 13 474 cm⁻¹ and 13 673 cm⁻¹ in the wavelength range 3100∼3300 Å. Ca II H, K absorption line doublets also clearly appear in the SDSS spectrum. All absorption lines show a similar blueshifted velocity structure of Δv ≈ − 1500 ∼ 0 km·s⁻¹ relative to the quasar's systematic redshift determined from the emission lines. Detailed analysis suggests that the Balmer absorption lines should arise from the partially ionized region with a column density of N_HI ≈ 10²¹ cm⁻² for an electron density of ne ∼ 10⁶ cm⁻³; and that the hydrogen n = 2 level may be populated via collisional excitation with Lyα pumping.     

Characteristics of Saturn’s FUV airglow from limb-viewing spectra obtained with Cassini-UVIS

This study reports the analysis of far ultraviolet (FUV) limb spectra of the airglow of Saturn in the 1150-1850 Å spectral window, obtained with the Ultraviolet Imaging Spectrograph (UVIS) onboard Cassini, spanning altitudes from −1200 to 4000 km. The FUV limb emission consists of three main contributions: (1) H Ly-α peaking at 1100 km with a brightness of 0.8 kilo-Rayleighs (kR), (2) reflected sunlight longward of 1550 Å which maximizes at −950 km with 16.5 kR and (3) H₂ bands in the 1150-1650 Å bandwidth, peaking at 1050 km reaching a maximum of 3.9 kR.A vertical profile of the local H₂ volume emission rate has been derived using the hydrocarbon density profiles from a model of the Saturn equatorial atmosphere. It is well matched by a Chapman function, characterized by a maximum value of 3.5 photons cm⁻³ s⁻¹ in the 800-1650 Å UV bandwidth, peaking at 1020 km.Comparisons between the observed spectra and a first-order synthetic airglow H₂ model in the 1150-1650 Å bandwidth show that the spectral shape of the H₂ bands is accounted for by solar fluorescence and photoelectron excitation. The best fits are obtained with a combination of H₂ fluorescence lines and 20 eV electron impact spectra, the latter contributing ∼68% of the total H₂ airglow emission.     

Europa's atmosphere, gas tori, and magnetospheric implications

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

Condensate clouds in Titan's north polar stratosphere

Analysis of the 250-560 cm⁻¹ spectral continuum of Titan's north polar hood just after spring equinox reveals, in addition to the ubiquitous aerosol, a tenuous but relatively uniform cloud of small particles permeating the lower stratosphere at altitudes between 58 and 90 km. Voyager 1 IRIS data suggest the particles are highly scattering, almost certainly condensed organics, with radii between 1 and 5 μm. Mole fractions for the condensed material range between 4×¹⁰⁻⁸ and 4×¹⁰⁻⁶, depending upon particle size. Vapor pressure arguments imply condensed nitriles near 90 km, the most likely being HCN, with condensed hydrocarbons such as C₂H₆ restricted to regions considerably nearer the tropopause. No direct chemical identification is possible. Negligible methane supersaturation in the troposphere at 67.4° N latitude, when compared with degrees of supersaturation at other latitudes, hints at precipitation fluxes of north polar stratospheric condensates during the previous northern winter that were perhaps three orders of magnitude greater than those at low latitudes during that time. A scale height of 1.5 times the density scale height above 160 km is reaffirmed for the photochemical aerosol of the north polar hood. There appears to be a depletion of aerosol somewhere below 160 km. An aerosol mole fraction ∼8×¹⁰⁻⁸ at 160 km is inferred, about 33% greater than the value derived in a previous study. The Cassini CIRS instrument, with its expanded spectral range and higher spectral resolution, should be able to provide highly complementary information for the time period covering most of the northern winter season.     

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

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

Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

Neutron Capture Isotopes in the Martian Regolith and Implications for Martian Atmospheric Noble Gases

Impact-produced glasses in some martian meteorites have trapped significant amounts of the recent martian atmosphere. From literature data, we estimate that ∼9% of the trapped ⁸⁰Kr in these meteorites was produced from neutron capture on ⁷⁹Br. Estimates of neutron fluences made from ⁸⁰Kr and ¹⁴⁹Sm for bulk samples of meteorite EET79001 indicate that ⁸⁰Kr excesses in the impact glass were not produced in situ. Theoretical calculations independently predict production of a large neutron-capture component of ⁸⁰Kr and ³⁶Ar in the martian regolith, and part of this component presumably escaped into the martian atmosphere. These calculations were made by using the Los Alamos High-Energy Transport Code to calculate the fluxes of galactic cosmic ray (GCR)-produced thermal neutrons as a function of depth in the uppermost 500 g cm⁻² of the martian surface, and by adopting average Cl, Br, and I concentrations of the upper martian surface of ∼0.3%, ∼20 ppm, and ∼0.5 ppm, respectively. Combining these data with the appropriate neutron-capture cross sections, we calculate Mars global production rates of ⁸⁰Kr_n=2.4×10¹⁶atoms sec⁻¹, ³⁶Ar_n=5.5×10¹⁸ atoms sec⁻¹, and ¹²⁸Xe_n=3×10¹³ atoms sec⁻¹. Calculated global production rates of spallogenic ⁸⁰Kr_sp, and ³⁶Ar_sp, are smaller by factors of ∼770 and ∼29, respectively. It would require ∼330 Myr to produce an amount of ⁸⁰Kr_n equivalent to the amount inferred to be present today in the martian atmosphere (∼2.5×10³² atoms). Production of these neutron-capture components probably has occurred over the past ∼4 Gyr, as only an atmospheric pressure substantially higher than today's would appreciably decrease the neutron flux in the regolith. Thus, most of the neutron-capture noble gases produced over time probably remain in the martian regolith and would make sensitive indicators of the time period a sample has resided near the martian surface. Assuming mixing of the martian surface to an average depth of 100 m, the predicted average regolith concentrations of ⁸⁰Kr_n, ³⁶Ar_n, and ¹²⁸Xe_n are ∼4×10⁻⁹ cm⁻³ g⁻¹, ∼1×10⁻⁶ cm³ g⁻¹, and ∼5×10⁻¹² cm³ g⁻¹, respectively. If similar fractions of these neutron-capture isotopes have escaped into the atmosphere, they would comprise ∼3% and ∼0.2% of the present atmospheric inventories of ³⁶Ar and ¹²⁸Xe, respectively. The fractional excess of ⁸⁰Kr_n in ancient martian meteorite ALH84001 appears similar to that in shock-glass phases of young shergottite meteorites. If ALH84001 acquired its atmospheric gases ∼4 Gyr ago, this implies that, prior to that time, halogens were greatly concentrated at the martian surface by crustal formational and weathering processes, impacts efficiently degassed the regolith, and Mars did not have a significant atmosphere to shield the surface.     

Predictions of the electrical conductivity and charging of the aerosols in Titan's atmosphere

The electrical conductivity and electrical charge on the aerosols in atmosphere of Titan are computed for altitudes from 0 to 400 km. Ionization due to both galactic cosmic rays and electron precipitation from the Saturnian magnetosphere is considered. This ionization results in free electrons and the primary ions N₂⁺ and N⁺ which are then rapidly converted into secondary ions such as H₂CN⁺ and NH₄⁺ which in turn form ion clusters such as H₂CN⁺(HCN)_n and NH₄⁺(NH₃)_m. In contrast to the atmospheres of Venus and Earth, we find no species in the Titan atmosphere that lead to the formation of appreciable concentrations of negative ions. Consequently, the predicted conductivity is quite different in that a substantial concentration of electrons exists all the way to the surface of Titan. The ubiquitous aerosols observed in the Titan atmosphere also play an important role in determining the charge distribution in the atmosphere. At altitudes above 100 km and for aerosol concentrations above approximately 10/cc, the recombination of electrons and positive ions is controlled by the recombination on the surface of the aerosols rather than by the gas-kinetic recombination rate. For small aerosol concentrations, the ratio of the number of charges per particle to the radius of the particle is approximately 30, for radii in microns. This value is similar to that obtained by previous investigators for terrestrial noctilucent clouds. Because the aerosol particles are highly charged, coagulation is inhibited, particle sizes are smaller, and their settling rates are reduced. As a consequence, the optical depth of the atmosphere is much higher than it would be if the particles were uncharged.     

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

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

Europa's Oxygen Exosphere and Its Magnetospheric Interaction

The newly detected oxygen atmosphere of Europa is modeled by invoking charged particle sputtering with H₂O and O₂molecules as the main ejecta. The magnetospheric corotating ions could provide the required source strength (∼3 × 10²⁶sec⁻¹) of O₂molecules if a fraction (∼20%) of the exospheric ions were recycled to Europa's surface where they produce additional sputtering product. Two exospheric components are expected to form: an extended corona with a size of a few satellite radii which is composed of sputtered molecules in ballistic motion, and a thermal population with a surface density of 10⁸–10⁹cm⁻³and a scale height of about 20 km. The electron impact ionization of this exosphere would lead to an Io-like interaction with the jovian magnetosphere with a field-aligned Birkeland current of about 5 × 10⁵A.