Distribution of minor constituents in a thermal interface

A non-steady, two-dimensional, compressible mathematical model of a fluid with constant viscosity and thermal conductivity is given in order to represent a thin atmospheric layer located at 60 km height, as a function of a known initial vertical distribution of temperature, chemical concentrations of minor components and assumed free boundary conditions.The purpose of this paper is to determine the influence of convective laminar processes in the vertical distribution of minor constituents in a thermal interface. Only three minor components are considered, atomic oxygen, molecular oxygen and ozone. Numerical solutions of the stated timedependent convection problem for different Rayleigh numbers show a marked influence of the established flow pattern upon the distribution of minor constituents. In all cases, an enhancement of mean concentration gradients in relatively small regions adjacent to the warmer and colder boundaries was observed.     

Detectability of minor constituents in the martian atmosphere by infrared and submillimeter spectroscopy

Spectroscopic remote sensing in the infrared and (sub)millimeter range is a powerful technique that is well suited for detecting minor species in planetary atmospheres (Planet Space Sci. 43(1995) 1485). Yet, only a handful of molecules in the Mars atmosphere (CO₂, CO and H₂O along with their isotopic species, O_3, and more recently H₂O₂ and CH₄) have been detected so far by this method. New high performance spectroscopic instruments will become available in the future in the infrared and (sub)millimeter range, for observations from the ground (infrared spectrometers on 8 m class telescopes, large millimeter and submillimeter interferometers) and from space, in particular the Planetary Fourier Spectrometer (PFS) aboard Mars Express (MEx), and the Heterodyne Instrument for the Far-Infrared (HIFI) aboard the Herschel Space Observatory (HSO). In this paper we will present results of a study that determines detectability of minor species in the atmosphere of Mars, taking into account the expected performance of the above spectroscopic instruments. In the near future, a new determination of the D/H value is expected with the PFS, especially during times of maximum H₂O abundance in the martian atmosphere. PFS is also expected to place constraints on the abundance of several minor species (H₂O₂,CH₄,CH₂O, SO₂, H₂S, OCS, HCl) above any local outgassing sources, the hot spots. It will be possible to obtain complementary information on some minor species (O₃,H₂O₂, CH₄) from ground-based infrared spectrometers on large telescopes. In the more distant future, HIFI will be ideally suited for measuring the isotopic ratios with unprecedented accuracy. Moreover, it should be able to observe O₂, which has not yet been detected spectroscopically in the IR/submm range, as well as H₂O₂. HIFI should also provide upper limits for several species that have not yet been detected (HCl, NH₃, PH₃) in the atmosphere of Mars. Some species (SO, SO₂,H₂S, OCS, CH₂O) that may be observable from the ground could be searched for with present single-dish antennae and arrays, and in the future with the Atacama Large Millimeter Array (ALMA) submillimeter interferometer.     

OH production rates in the troposphere

The evaluation of OH radical reactions as a global sink for many trace gases in the troposphere requires a detailed knowledge of the OH production rate as a function of latitude and altitude. The OH production rate may be expressed as a product of the primary rate P₁ from the reaction of O(¹D) with water vapor and an amplification factor ? due to a re-cycling mechanism. The primary rate and its diurnal and seasonal averages have been computed as a function of latitude and altitude for the northern hemisphere, using only observational data for the involved parameters. For the southern hemisphere this procedure is not possible at present, because sufficiently detailed ozone measurements are not available. The calculation of the amplification factor requires in addition to the latitudinal distributions of atmospheric mixing ratios of CH₄ and CO, those of nitrogen dioxide for which observational data are almost entirely lacking. Accordingly the distribution of NO₂ mixing ratios was estimated to obtain values for the amplification factor ?. Effective OH production rates are given assuming that primary OH production rates obtained for the northern hemisphere are applicable also in the southern hemisphere. Due to the many uncertainties entering specifically into the values for the amplification factor the derived OH production rates must be considered a first approximation.     

Photochemistry of the Martian atmosphere

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

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO₂H₂ON₂ atmosphere on Mars and estimates are given for the concentrations of N, NO, NO₂, NO₃, N₂O₅, HNO₂, HNO₃, and N₂O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO₂ of order 10^?8. Deposition rates for nitrite and nitrate minerals could be as large as 3× 10⁵ N equivalent atoms cm^?2 sec^?1 under present conditions and may have been higher in the past.     

First model of negative ion composition in the troposphere

A chemical model of negative ions in the troposhere (0–15 km) is presented. This model is an extension of the negative ion composition model in the lower stratosphere (Kawamoto and Ogawa, 1984, Planet. Space Sci. 32, 1223) with some modifications. The computed result shows that the predominant ions are NO₃⁻HNO₃H₂O below 10km and NO⁻₃(HNO₃)₂ above 10km, and that the fractional abundance of cluster ions having a HSO⁻₄ core increases with height below 12km and decreases with height above it. The ions having CO⁻₃ cores are at most 2% in fractional abundance. The other kinds of negative ions are far smaller in fractional abundance than the NO⁻₃, HSO⁻₄ and CO⁻₃ core ions. The result is compared with the two mass spectrometric observed results (Heitmann and Arnold, 1983, Nature, Lond. 306, 747; Perkins and Eisele, 1984, J. geophys. Res. 89, 9649). The problems on the tropospheric negative ions which arose are discussed.     

Photochemistry of flourine in the mesosphere of Venus

In the laboratory, reactions with flourine species proceed rapidly with high rates but under mesospheric conditions the effeciency of these compounds is low due to the rapid formation of HF and to the lack of reactivity of this species. Even if diffusion processes are included, the result of calculations leads to fluorie concentrations typically less than 20 cm^?3. The low photodissociation coeffecient of HF leads to the expectation of a scale height of HF greater than or equal to the mean scale height. If the troposphere appears to be a sink for hydrofluoric acid, the maximum value of fluorine is obtained with a downward flux of 1.3 × 10⁸ HF atoms cm^?2 sec^?1 at the level of the clouds.     

Insolation in Titan’s troposphere

Seasonality in Titan’s troposphere is driven by latitudinally varying insolation. We show that the latitudinal distributions of insolation in the troposphere and at the surface, based on Huygens DISR measurements, can be approximated analytically with nonzero extinction optical depths τ, and are not equivalent to that at the top of the atmosphere (τ = 0), as has been assumed previously. This has implications for the temperature distribution and the circulation, which we explore with a simple box model. The surface temperature maximum and the upwelling arm of thermally-direct meridional circulation reach the midlatitudes, not the poles, during summertime.     

Recognition of minor constituents in reflectance spectra of Allan Hills 84001 chips and the importance for remote sensing on Mars

Abstract— Reflectance spectra of splits 92 and 271 from the Martian meteorite Allan Hills (ALH) 84001 are presented and analyzed in this paper. Although the visible and infrared spectra of both chips show that the dominant mineralogy is low-Ca pyroxene, the focus here is on identification of the minor constituents. Infrared spectra measured at multiple spots along the surface of chips 92 and 271 show subtle spectroscopic variations due to changes in the low-Ca pyroxene texture and composition and to the presence of secondary minerals. Absorption bands observed near 0.93 and 1.95 μm are characteristic of low-Ca pyroxene. Strong mid-infrared reststrahlen bands are observed near 9 and 19.5 μm in all surface spectra, and additional bands near 7, 10.5, 11.4, 17.8, 20.5 and 23 μm are variable depending on the low-Ca pyroxene texture and the presence of secondary minerals. Selected spectra exhibit carbonate features near 4, 6.4–7.1 and 11.3 μm. Detailed analysis of these carbonate features indicates the presence of Mg-Fe carbonate, which is consistent with petrographic studies. Many of these spectra with strong carbonate features exhibit a magnetite feature near 17.9 μm and a shoulder near 20.5 μm that cannot be uniquely ascribed to one mineral. Spectroscopic identification of the minor carbonate and magnetite minerals in this probable piece of Mars indicates that detection of small amounts of these minerals of possible biological significance will be possible using infrared hyperspectral analyses of the Martian surface. Also of importance for remote sensing on Mars is the result that Mg, Fe and Mg-Fe carbonates in a low-Ca pyroxene matrix should be distinguishable from one another in the spectral region measured by the thermal emmitance spectrometer (TES).     

Ground-based near-infrared observations of water vapour in the Venus troposphere

We present a study of water vapour in the Venus troposphere obtained by modelling specific water vapour absorption bands within the 1.18 μm window. We compare the results with the normal technique of obtaining the abundance by matching the peak of the 1.18 μm window. Ground-based infrared imaging spectroscopy of the night side of Venus was obtained with the Anglo-Australian Telescope and IRIS2 instrument with a spectral resolving power of R ～ 2400. The spectra have been fitted with modelled spectra simulated using the radiative transfer model VSTAR. We find a best fit abundance of 31 ppmv (?6 +9 ppmv), which is in agreement with recent results by Bézard et al. (Bézard, B., Fedorova, A., Bertaux, J.-L., Rodin, A., Korablev, O. [2011]. Icarus, 216, 173–183) using VEX/SPICAV (R ～ 1700) and contrary to prior results by Bézard et al. (Bézard, B., de Bergh, C., Crisp, D., Maillard, J.P. [1990]. Nature, 345, 508–511) of 44 ppmv (±9 ppmv) using VEX/VIRTIS-M (R ～ 200) data analyses. Comparison studies are made between water vapour abundances determined from the peak of the 1.18 μm window and abundances determined from different water vapour absorption features within the near infrared window. We find that water vapour abundances determined over the peak of the 1. 18 μm window results in plots with less scatter than those of the individual water vapour features and that analyses conducted over some individual water vapour features are more sensitive to variation in water vapour than those over the peak of the 1. 18 μm window. No evidence for horizontal spatial variations across the night side of the disk are found within the limits of our data with the exception of a possible small decrease in water vapour from the equator to the north pole. We present spectral ratios that show water vapour absorption from within the lowest 4 km of the Venus atmosphere only, and discuss the possible existence of a decreasing water vapour concentration towards the surface.     

Coupling of acoustic waves to clouds in the jovian troposphere

Seismology is the best tool for investigating the interior structure of stars and giant planets. This paper deals with a photometric study of jovian global oscillations. The propagation of acoustic waves in the jovian troposphere is revisited in order to estimate their effects on the planetary albedo. According to the standard model of the jovian cloud structure there are three major ice cloud layers (e.g., [Atreya et al., 1999. A comparison of the atmospheres of Jupiter and Saturn: Deep atmospheric composition, cloud structure, vertical mixing, and origin. Planet Space Sci. 47, 1243-1262]). We consider only the highest layers, composed of ammonia ice, in the region where acoustic waves are trapped in Jupiter's atmosphere. For a vertical wave propagating in a plane parallel atmosphere with an ammonia ice cloud layer, we calculate first the relative variations of the reflected solar flux due to the smooth oscillations at about the ppm level. We then determine the phase transitions induced by the seismic waves in the clouds. These phase changes, linked to ice particle growth, are limited by kinetics. A Mie model [Mishchenko et al., 2002. Scattering, Absorption, and Emission of Light by Small Particles. Cambridge Univ. Press, Cambridge, pp. 158-190] coupled with a simple radiation transfer model allows us to estimate that the albedo fluctuations of the cloud perturbed by a seismic wave reach relative variations of 70 ppm for a 3-mHz wave. This albedo fluctuation is amplified by a factor of ∼70 relative to the previously published estimates that exclude the effect of the wave on cloud properties. Our computed amplifications imply that jovian oscillations can be detected with very precise photometry, as proposed by the microsatellite JOVIS project, which is dedicated to photometric seismology [Mosser et al., 2004. JOVIS: A microsatellite dedicated to the seismic analysis of Jupiter. In: Combes, F., Barret, D., Contini, T., Meynadier, F., Pagani, L. (Eds.), SF2A-2004, Semaine de l'Astrophysique Francaise, Les Ulis. In: EdP-Sciences Conference Series, pp. 257-258].     

Recombination of small ions in the troposphere and lower stratosphere

The current practice of treating ionic recombination in the lower atmosphere is in error in two respects: firstly the Thomson formula for the ter-molecular recombination coefficient does not represent the behaviour as accurately as commonly assumed: secondly the ter-molecular recombination coefficient (expressed in binary form) and the rate coefficient for the binary recombination of an isolated ion-pair are not additive. Computer simulated experiments are performed which should give the total recombination coefficient in the region below 40 km with some precision. It is shown that the recombination rate is not appreciably affected by inhomogeneity in the cosmic ray ionization. The equilibrium small ion number density profile is calculated and found to be in good agreement with the observed profile. It is inferred that the mixing ratio of the trace gas x which reacts with proton hydrates to form non-proton hydrates has an approximately constant value of 5 × 10⁻¹³ from 20 to 42 km.     

Carbon dioxide and monoxide above the troposphere

The dependence of the atmospheric distributions of CO₂ and CO upon the combined effects of photochemical production and loss, and transport is examined. It is found that, for CO₂, deviations from complete mixing are possible in the mesosphere and upper stratosphere. Further, sufficient quantities of CO may be maintained, as a product of CO₂ photodissociation, to be aeronomically significant.     

First composition measurements of positive ions in the upper troposphere

First mass-spectrometric composition measurements of atmospheric ions between 3250 and 11700 m altitude are reported. They reveal the presence of very massive cluster ions, the majority of which cannot be attributed to a single hydrated ion family like, for example H⁺(H₂O)_n. The observed fraction of very massive ions increases with decreasing altitude. Masses as large as about 540 amu were observed at 8200 m altitude. Implications of the observations for ion and nucleation processes are discussed.     

Photochemistry of methane-water ices

We report a study on the broadband ultraviolet photolysis of methane-water ice mixtures, at low methane concentrations and temperatures relevant to the icy satellites of the outer Solar System. The photochemistry of these mixtures is dominated by the action of hydroxyl radicals on methane and the resulting products. This implies that, given sufficient exposure time, the methane will eventually be completely oxidized to carbon dioxide. The presence of methane inhibits the formation of hydrogen peroxide by serving as a trap for hydroxyl radicals. The distribution of photochemical products is broadly similar to that previously conducted using ion and electron sources, with some differences possibly attributable to the difference in radiation source. The results are applicable to a variety of icy bodies in the Solar System. On Enceladus, where methane mixed with water is measured in the plumes, methane in the surface ices is subject to oxidation and will eventually be converted to CO₂. The CH stretch feature detected in the VIMS spectra of the Enceladus surface ice suggests that methane is currently being supplied to the surface ice, likely from re-condensation of the plume gas.     

Chemical reactions in the Titan’s troposphere during lightning

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH₄/N₂ atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H₂, HCN, C₂N₂, C₂H₂, C₂H₄, C₂H₆, NH₃ and H₂CN. The annual production of these compounds was estimated in the Titan’s atmosphere.     

Moist convection and the abundance of water in the troposphere of Jupiter

A model for narrow moist convective plumes in the lower troposphere of Jupiter can reconcile the apparent depletion of water in that region of the atmosphere with a near-solar abundance of oxygen throughout the interior.     

Long-term changes in Saturn's troposphere

We report the results of monitoring Saturn's H₂ quadrupole and CH₄ band absorptions outside of the equatorial zone over one-half of Saturn's year. This interval covers most of the perihelion half of Saturn's elliptical orbit, which happens to be approximately bounded by the equinoxes. Marked long-term changes occur in the CH₄ absorption accompanied by weakly opposite changes in the H₂ absorption. Around the 1980 equinox, the H₂ and CH₄ absorptions in the northern hemisphere appear to be discontinuous with those in the southern hemisphere. This discontinuity and the temporal variation of the absorptions are evidence for seasonal changes. The absorption variations can be attributed to a variable haze in Saturn's troposphere, responding to changes in temperature and insolation through the processes of sublimation and freezing. Condensed or frozen CH₄ is very unlikely to contribute any haze. The temporal variation of the absorption in the strong CH₄ bands at south temperate latitudes is consistent with a theoretically expected phase lag of 60° between the tropopause temperature and the seasonally variable insolation. We model the vertical haze distribution of Saturn's south temperature latitudes during 1971–1977 in terms of a distribution having a particle scale height equal to a fraction of the atmospheric scale height. The results are a CH₄/H₂ mixing ratio of (4.2 ± 0.4) × 10^?3, a haze particle albedo of $\text{ω}\text{= 0.995 ± 0.003}$, and a range of variation in the particle to gas scale-height ratio of 0.6 ± 0.2. The haze was lowest near the time of maximum temperature. We also report spatial measurements of the absorption in the 6450 Å NH₃ band made annually since the 1980 equinox. A 20 ± 4% increase in the NH₃ absorption at south temperate latitudes has occurred since 1973–1976 and the NH₃ absorption at high northern latitudes has increased during spring. Increasing insolation, and the resulting net sublimation of NH₃ crystals, is probably the cause. Significant long-term changes apparently extend to the deepest visible parts of Saturn's atmosphere. An apparently anomalous ortho-para H₂ ratio in 1978 suggests that the southern temperate latitudes experienced an unusual upwelling during that time. This may have signaled a rise in the radiative-convective boundary from deep levels following maximum tropospheric temperature and the associated maximum radiative stability. This would be further evidence that the deep, visible atmosphere is governed by processes such as dynamics and the thermodynamics of phase changes, which have response times much shorter than the radiative time constant.     

Temperature lapse rate and methane in Titan's troposphere

We have reanalyzed the Voyager radio occultation data for Titan, examining two alternative approaches to methane condensation. In one approach, methane condensation is facilitated by the presence of nitrogen because nitrogen lowers the condensation level of a methane/nitrogen mixture. The resulting enhancement in methane condensation lowers the upper limit on surface relative humidity of methane obtained from the Voyager occultation data from 0.7 to 0.6. We conclude that in this case the surface relative humidity of methane lies between 0.08 and 0.6, with values close to 0.6 indicated. In the other approach, methane is allowed to become supersaturated and reaches 1.4 times saturation in the troposphere. In this case, surface humidities up to 100% are allowed by the Voyager occultation data, and thus the upper limit must be set by other considerations. We conclude that if supersaturation is included, then the surface relative humidity of methane can be any value greater than 0.08--unless a deep ocean is present, in which case the surface relative humidity is limited to less than 0.85. Again, values close to 0.6 are indicated. Overall, the tropospheric lapse rate on Titan appears to be determined by radiative equilibrium. The lapse rate is everywhere stable against dry convection, but is unstable to moist convection. This finding is consistent with a supersaturated atmosphere in which condensation-and hence moist convection-is inhibited.     

Cassini CIRS retrievals of ammonia in Jupiter's upper troposphere

The zonal mean ammonia abundance on Jupiter between the 400- and 500-mbar pressure levels is inferred as a function of latitude from Cassini Composite Infrared Spectrometer data. Near the Great Red Spot, the ammonia abundance is mapped as a function of latitude and longitude. The Equatorial Zone is rich in ammonia, with a relative humidity near unity. The North and South Equatorial Belts are depleted relative to the Equatorial Zone by an order of magnitude. The Great Red Spot shows a local maximum in the ammonia abundance. Ammonia abundance is highly correlated with temperature perturbations at the same altitude. Under the assumption that anomalies in ammonia and temperature are both perturbed from equilibrium by vertical motion, we find that the adjustment time constant for ammonia equilibration is about one third of the radiative time constant.