Comment on “Methane on Mars: A product of H2O photolysis in the presence of CO” by A. Bar-Nun and V. Dimitrov

Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322] suggested a sequence of reactions to form methane on Mars. These reactions are based on the study of products in the N₂-CO-H₂O mixture irradiated at 185 nm. The suggested scheme was not quantitatively justified by chemical kinetics. One of the key reactions is effectively blocked by O₂ in the martian atmosphere, and another key reaction does not exist. There are no pathways for effective formation of methane in the martian atmosphere.     

Methane on Mars: A product of H2O photolysis in the presence of CO

We suggest that the methane observed on Mars can be formed by photolysis of water vapor in the presence of CO, in addition to possible geological sources, rather than biologically.     

Ozone abundance on Mars from infrared heterodyne spectra: II. Validating photochemical models

Ozone is an important observable tracer of martian photochemistry, including odd hydrogen (HO_x) species important to the chemistry and stability of the martian atmosphere. Infrared heterodyne spectroscopy with spectral resolution ?¹⁰⁶ provides the only ground-based direct access to ozone absorption features in the martian atmosphere. Ozone abundances were measured with the Goddard Infrared Heterodyne Spectrometer and the Heterodyne Instrument for Planetary Wind and Composition at the NASA Infrared Telescope Facility on Mauna Kea, Hawai'i. Retrieved total ozone column abundances from various latitudes and orbital positions (LS=40°, 74°, 102°, 115°, 202°, 208°, 291°) are compared to those predicted by the first three-dimensional gas phase photochemical model of the martian atmosphere [Lefèvre, F., Lebonnois, S., Montmessin, F., Forget, F., 2004. J. Geophys. Res. 109, doi:10.1029/2004JE002268. E07004]. Observed and modeled ozone abundances show good agreement at all latitudes at perihelion orbital positions (LS=202°, 208°, 291°). Observed low-latitude ozone abundances are significantly higher than those predicted by the model at aphelion orbital positions (LS=40°, 74°, 115°). Heterogeneous loss of odd hydrogen onto water ice cloud particles would explain the discrepancy, as clouds are observed at low latitudes around aphelion on Mars.     

Simultaneous mapping of H2O and H2O2 on Mars from infrared high-resolution imaging spectroscopy

New maps of martian water vapor and hydrogen peroxide have been obtained in November-December 2005, using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infra Red Telescope facility (IRTF) at Mauna Kea Observatory. The solar longitude Ls was 332° (end of southern summer). Data have been obtained at 1235-1243 cm⁻¹, with a spectral resolution of 0.016 cm⁻¹ (R=8×¹⁰⁴). The mean water vapor mixing ratio in the region [0°-55° S; 345°-45° W], at the evening limb, is 150±50 ppm (corresponding to a column density of 8.3±2.8 pr-μm). The mean water vapor abundance derived from our measurements is in global overall agreement with the TES and Mars Express results, as well as the GCM models, however its spatial distribution looks different from the GCM predictions, with evidence for an enhancement at low latitudes toward the evening side. The inferred mean H₂O₂ abundance is 15±10 ppb, which is significantly lower than the June 2003 result [Encrenaz, T., Bézard, B., Greathouse, T.K., Richter, M.J., Lacy, J.H., Atreya, S.K., Wong, A.S., Lebonnois, S., Lefèvre, F., Forget, F., 2004. Icarus 170, 424-429] and lower than expected from the photochemical models, taking in account the change in season. Its spatial distribution shows some similarities with the map predicted by the GCM but the discrepancy in the H₂O₂ abundance remains to be understood and modeled.     

Infrared imaging spectroscopy of Mars: H2O mapping and determination of CO2 isotopic ratios

High-resolution infrared imaging spectroscopy of Mars has been achieved at the NASA Infrared Telescope Facility (IRTF) on June 19-21, 2003, using the Texas Echelon Cross Echelle Spectrograph (TEXES). The areocentric longitude was 206°. Following the detection and mapping of hydrogen peroxide H₂O₂ [Encrenaz et al., 2004. Icarus 170, 424-429], we have derived, using the same data set, a map of the water vapor abundance. The results appear in good overall agreement with the TES results and with the predictions of the Global Circulation Model (GCM) developed at the Laboratory of Dynamical Meteorology (LMD), with a maximum abundance of water vapor of 3±1.5×¹⁰⁻⁴(17±9 pr-μm). We have searched for CH₄ over the martian disk, but were unable to detect it. Our upper limits are consistent with earlier reports on the methane abundance on Mars. Finally, we have obtained new measurements of CO₂ isotopic ratios in Mars. As compared to the terrestrial values, these values are: (¹⁸O/¹⁷O)[M/E] = 1.03 ± 0.09; (¹³C/¹²C)[M/E] = 1.00 ± 0.11. In conclusion, in contrast with the analysis of Krasnopolsky et al. [1996. Icarus 124, 553-568], we conclude that the derived martian isotopic ratios do not show evidence for a departure from their terrestrial values.     

Ozone abundance on Mars from infrared heterodyne spectra: I. Acquisition, retrieval, and anticorrelation with water vapor

Observations of ozone on Mars were made using the Goddard Space Flight Center's Infrared Heterodyne Spectrometer and Heterodyne Instrument for Planetary Wind and Composition at the NASA Infrared Telescope Facility. Ozone is an important observable tracer of martian photochemistry. Infrared heterodyne spectroscopy with spectral resolution ?¹⁰⁶ is the only technique that directly measures ozone in the martian atmosphere from the surface of the Earth. Ozone column abundances down to the martian surface were acquired in seven data sets taken between 1988 and 2003 at various orbital positions (LS=40°, 74°, 102°, 115°, 202°, 208°, 291°). Ozone abundances are compared with those retrieved using ultraviolet techniques, showing good agreement. Odd hydrogen (HO_X) chemistry predicts anticorrelation of ozone and water vapor abundances. Retrieved ozone abundances consistently show anticorrelation with corresponding water vapor abundances, providing strong confirmation of odd hydrogen activity. Deviation from strict anticorrelation between the observed total column densities of ozone and water vapor suggests that constituent vertical distribution is an additional, significant factor.     

Airglow on Mars: Some model expectations for the OH Meinel bands and the O2 IR atmospheric band

This work presents model calculations of the diurnal airglow emissions from the OH Meinel bands and the O₂ IR atmospheric band in the neutral atmosphere of Mars. A time-dependent photochemical model of the lower atmosphere below 80 km has been developed for this purpose. Special emphasis is placed on the nightglow emissions because of their potential to characterize the atomic oxygen profile in the 50-80 km region. Unlike on Earth, the OH Meinel emission rates are very sensitive to the details of the vibrational relaxation pathway. In the sudden death and collisional cascade limits, the maximum OH Meinel column intensities for emissions originating from a fixed upper vibrational level are calculated to be about 300 R, for transitions v^′=9→v^′?8, and 15,000 R, for transitions v^′=1→v^′=0, respectively. During the daytime the 1.27 μm emission from O₂(), primarily formed from ozone photodissociation, is of the order of MegaRayleighs (MR). Due to the long radiative lifetime of O₂(), a luminescent remnant of the dayglow extends to the dark side for about two hours. At night, excited molecular oxygen is expected to be produced through the three body reaction O + O + CO₂. The column emission of this nighttime component of the airglow is estimated to amount to 25 kR. Both nightglow emissions, from the OH Meinel bands and the O₂ IR atmospheric band, overlap in the 50-80 km region. Photodissociation of CO₂ in the upper atmosphere and the subsequent transport of the atomic oxygen produced to the emitting layer are revealed as key factors in the nightglow emissions from these systems. The Mars 5 upper constraint for the product [H][O₃] is revised on the basis of more recent values for the emission probabilities and collisional deactivation coefficients.     

The jovian anticyclone BA: I. Motions and interaction with the GRS from observations and non-linear simulations

A study of the dynamics of the second largest anticyclone in Jupiter, Oval BA, and its red colour change that occurred in late 2005 is presented in a three part study. The first part, this paper, deals with its long-term kinematical and dynamical behaviour monitored since its formation in 2000 to September 2008 using ground-based observations archived at the public International Outer Planet Watch (IOPW) database. The vortex changed its zonal drift velocity from 1.8 m s⁻¹ in the period 2000-2002 to 0.8 m s⁻¹ in 2002-2003, and to 2.5 m s⁻¹ since late 2003. It also migrated southwards by 1.0 ± 0.5° in latitude between 2000 and 2004, remaining afterwards at an almost fixed latitude position. During the period 2000-2007, the oval also changed its triangular-like shape to a more symmetrical one. No latitudinal change was found in the months before the development of a red annulus in its interior. The colour change took place in less than 5 months in 2005-2006 and no red colour feature was observed to have been present or entrained by BA months before the annulus development. After detailed examination of the four encounters between BA and GRS that took place during this 9 year period, we did not detect any noticeable change in its drift rate or in apparent structure associated with the encounters at cloud level. Also, the area of BA did not significantly change in this period. Additionally, we found that BA displays a long-term oscillation of ∼160 days in its longitude position with peak to peak amplitude of 1.2°. Numerical experiments using the global circulation model EPIC reproduce accurately the shape, connecting it to its latitude migration, and morphology of the oval and confirm that no strong interaction between BA and the GRS is possible at least in the current situation.     

Mapping of Mars O2 1.27 μm dayglow at four seasonal points

The O₂ dayglow at 1.27 μm is formed by high-altitude ozone on Mars and is a sensitive tracer of Mars photochemistry. Mapping of this dayglow using the IRTF/CSHELL long-slit spectrograph requires the extraction of weak emission lines against a strong continuum of the reflected solar light. Some new tools are suggested to improve the data processing. The observed O₂ dayglow intensities at L_S=67°, 112°, 148°, and 173° show a decrease from late spring (aphelion) to fall equinox by a factor of ≈5 at low latitudes (±30°). This decrease agrees with that predicted by a model of Clancy and Nair (1996, J. Geophys. Res. 101 (12) 12785-12790), although the dayglow intensities are weaker than those based on that model. The measured dayglow variations with latitude are rather low at L_S=67°, 112°, and 148° and unexpectedly high at 173°. The dayglow intensity peaks near noon and is smaller at 9:00 and 16:30 LT by a factor of 2. Some data on the ozone profile near aphelion are obtained from a combination of the dayglow and ozone observations. It is hardly possible to detect the O₂ night airglow at 1.27 μm on Mars using the existing ground-based and on-orbit instruments. The O₂ dayglow intensity as a function of latitude and season from aphelion to fall equinox has been obtained. Our goal is to extend this distribution to the full martian year and get a database for Mars photochemistry to complement the MGS/TES observations of water vapor, atmospheric temperature, and dust and ice aerosol.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: II. Results from a coupled dynamics-microphysics-photochemistry GCM

We present a 2D general circulation model of Titan's atmosphere, coupling axisymmetric dynamics with haze microphysics, a simplified photochemistry and eddy mixing. We develop a parameterization of latitudinal eddy mixing by barotropic waves based on a shallow-water, longitude-latitude model. The parameterization acts locally and in real time both on passive tracers and momentum. The mixing coefficient varies exponentially with a measure of the barotropic instability of the mean zonal flow. The coupled GCM approximately reproduces the Voyager temperature measurements and the latitudinal contrasts in the distributions of HCN and C₂H₂, as well as the main features of the zonal wind retrieved from the 1989 stellar occultation. Wind velocities are consistent with the observed reversal time of the North-South albedo asymmetry of 5 terrestrial years. Model results support the hypothesis of a non-uniform distribution of infrared opacity as the cause of the Voyager temperature asymmetry. Transport by the mean meridional circulation, combined with polar vortex isolation may be at the origin of the latitudinal contrasts of trace species, with eddy mixing remaining restricted to low latitudes most of the Titan year. We interpret the contrasts as a signature of non-axisymmetric motions.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: I. General properties from a horizontal shallow-water model

We present a numerical study of barotropic waves in Titan's stratosphere based on a shallow-water model. The forcing of the zonal flow by the mean meridional circulation is represented by a relaxation towards a barotropically unstable wind profile. The relaxation profile is consistent with observations and with previous results from a 3D general circulation model. The time constant of the forcing that best matches the northward eddy-transport of zonal momentum from the 3D model is τ∼5 Titan days. The eddy wind field is a zonal wavenumber-2 wave with a peak amplitude about 10% of the mean wind speed. The latitudinal transport of angular momentum by the wave tends to keep the flow close to marginal stability by carrying momentum upgradient, from the core of the jets into the low latitudes. Although the strongest eddy motions occur at the latitudes of the wind maxima, the strongest mixing takes place at the barotropically unstable regions, close to ±30° and spanning about 30° in latitude. An eddy-mixing time constant of the order of 1 Titan day is inferred within these regions, and of a few tens of days within regions of stable flow. Horizontal gradients in transient tracer fields are less than 10% of the latitudinal gradient of the meridional tracer profile. Cassini's detection of such waves could provide a direct observation of wind speeds at stratospheric levels.     

Loss of water from Mars:: Implications for the oxidation of the soil

The evolution of the martian atmosphere with regard to its H₂O inventory is influenced by thermal loss processes of H, H₂, nonthermal atmospheric loss processes of H⁺, H₂⁺, O, O⁺, CO₂, and O₂⁺ into space, as well as by chemical weathering of the surface soil. The evolution of thermal and nonthermal escape processes depend on the history of the intensity of the solar XUV radiation and the solar wind density. Thus, we use actual data from the observation of solar proxies with different ages from the Sun in Time program for reconstructing the Sun's radiation and particle environment from the present to 3.5 Gyr ago. The correlation between mass loss and X-ray surface flux of solar proxies follows a power law relationship, which indicates a solar wind density up to 1000 times higher at the beginning of the Sun's main sequence lifetime. For the study of various atmospheric escape processes we used a gas dynamic test particle model for the estimation of the pick up ion loss rates and considered pick up ion sputtering, as well as dissociative recombination. The loss of H₂O from Mars over the last 3.5 Gyr was estimated to be equivalent to a global martian H₂O ocean with a depth of about 12 m, which is smaller than the values reported by previous studies. If ion momentum transport, a process studied in detail by Mars Express is significant on Mars, the water loss may be enhanced by a factor of about 2. In our investigation we found that the sum of thermal and nonthermal atmospheric loss rates of H and all nonthermal escape processes of O to space are not compatible with a ratio of 2:1, and is currently close to about 20:1. Escape to space cannot therefore be the only sink for oxygen on Mars. Our results suggest that the missing oxygen (needed for the validation of the 2:1 ratio between H and O) can be explained by the incorporation into the martian surface by chemical weathering processes since the onset of intense oxidation about 2 Gyr ago. Based on the evolution of the atmosphere-surface-interaction on Mars, an overall global surface sink of about 2×10⁴² oxygen particles in the regolith can be expected. Because of the intense oxidation of inorganic matter, this process may have led to the formation of considerable amounts of sulfates and ferric oxides on Mars. To model this effect we consider several factors: (1) the amount of incorporated oxygen, (2) the inorganic composition of the martian soil and (3) meteoritic gardening. We show that the oxygen incorporation has also implications for the oxidant extinction depth, which is an important parameter to determine required sampling depths on Mars aimed at finding putative organic material. We found that the oxidant extinction depth is expected to lie in a range between 2 and 5 m for global mean values.     

Saturn's auroral/polar H3 infrared emission: II. A comparison with plasma flow models

We present a detailed analysis of the H⁺₃ intensity and velocity profiles crossing Saturn's auroral/polar region, as described by Stallard et al. [Stallard, T., Miller, S., Melin, H., Lystrup, M., Dougherty, M., Achilleos, N., 2007. Icarus 189, 1-13], with a view to understanding the magnetospheric processes with which they are connected. The data are not consistent with the theory that Saturn's main auroral oval is associated with corotation enforcement currents in the middle magnetosphere. This implies that the main auroral oval can be associated with the open-closed field line boundary [Cowley, S.W.H., Bunce, E.J., O'Rourke, J.M., 2004. J. Geophys. Res. 109. A05212]; a third model, by Sittler et al. [Sittler, E.C., Blanc, M.F., Richardson, J.D., 2006. J. Geophys. Res. 111. A06208] associates the main oval with centrifugal instabilities in the outer magnetosphere, but does not make predictions about ionospheric plasma flows with which we can compare our data. We do, however, tentatively identify emission at latitudes lower than the main auroral oval which may be associated with the corotation enforcement currents in the middle magnetosphere. We also find that at latitudes higher than the main auroral oval there is often a region of the ionosphere that is in rigid corotation with the planet. We suggest that this region corresponds to field lines embedded in the centre of the magnetotail which are shielded from the solar wind such that their rotation is controlled only by the neutral atmosphere.     

Interannual Variability of Martian Global Dust Storms: Simulations with a Low-Order Model of the General Circulation

We present simulations of the interannual variability of martian global dust storms (GDSs) with a simplified low-order model (LOM) of the general circulation. The simplified model allows one to conduct computationally fast long-term simulations of the martian climate system. The LOM is constructed by Galerkin projection of a 2D (zonally averaged) general circulation model (GCM) onto a truncated set of basis functions. The resulting LOM consists of 12 coupled nonlinear ordinary differential equations describing atmospheric dynamics and dust transport within the Hadley cell. The forcing of the model is described by simplified physics based on Newtonian cooling and Rayleigh friction. The atmosphere and surface are coupled: atmospheric heating depends on the dustiness of the atmosphere, and the surface dust source depends on the strength of the atmospheric winds. Parameters of the model are tuned to fit the output of the NASA AMES GCM and the fit is generally very good.Interannual variability of GDSs is possible in the LOM, but only when stochastic forcing is added to the model. The stochastic forcing could be provided by transient weather systems or some surface process such as redistribution of the sand particles in storm generating zones on the surface. The results are sensitive to the value of the saltation threshold, which hints at a possible feedback between saltation threshold and dust storm activity. According to this hypothesis, erodable material builds up as a result of a local process, whose effect is to lower the saltation threshold until a GDS occurs. The saltation threshold adjusts its value so that dust storms are barely able to occur.     

Possible long-term decline in impact rates: 1. Martian geological data

Quantin et al. [Quantin, C., Allemand, P., Mangold, N., Delacourt, C., 2004a. Icarus 172, 555-572] tabulated crater count data for 56 landslides along the walls of Valles Marineris. Under the assumption of a constant cratering rate after about 3 Gyr ago, as used in the 1999-2005 iterations of the crater chronology isochron system of Hartmann, and in the Hartmann and Neukum system, these data indicate a regularly increasing rate of landslides, which would be difficult to explain. We suggest that these data may support a decline in inner Solar System cratering rates by about a factor of 3 since 3 Gyr ago, not unlike predictions based on asteroid belt collision models. Such a decline is also supported by our review of data on lunar impact melts and glass spherules in a companion paper [Hartmann, W.K., Quantin, C., Mangold, N., 2007. Icarus 186, 11-23]. Such models produce not only a more uniform rate of landslides over the last 3 Gyr, but also a more uniform rate of resurfacing processes which also had an apparent increase under the assumption of a constant cratering rate.     

The jovian anticyclone BA: III. Aerosol properties and color change

A study of the vertical cloud structure of oval BA and its red color change is presented in this third part of our complete analysis. A large interest in Jupiter’s anticyclone BA was created by its reddening that occurred between 2005 and 2006. In this work we quantify the color change in oval BA by using images taken with the Advanced Camera for Surveys (ACS) onboard the Hubble Space Telescope (HST) in six filters from the near ultraviolet (F250W) to the deep methane band in the near infrared (F892N). Reflectivity changes are noteworthy in nadir viewing geometry at the ultraviolet and blue wavelengths (F250W, F330W and F435W filters) but almost undetectable or inside error bars in the rest of filters (F550M, F658N and F892N). The observed reflectivity variations are discussed in terms of a commonly accepted vertical cloud structure model for jovian anticyclones in order to explore some causes for the color alteration. Our models of the observed reflectivity variation show that the vortex clouds did not change its vertical extension (top pressure) or its optical depth. We find that a change occurred in the absorbing properties of the particles populating the upper aerosols (single scattering albedo and imaginary refractive index). A discussion on the thermo-physical and dynamical properties of the vortex that could be in the origin of the color change is also presented.     

Corona-like atmospheric escape from KBOs: II. The behavior of aerosols

In Levi and Podolak (Levi, A., Podolak, M. [in press] Icarus) we applied the theory of coronal expansion to gas escape from a small, cold, object such as those found in the Kuiper belt. Here we extend the theory to include aerosols that are lifted off the surface by the escaping gas. Aerosols carried by the gas but still gravitationally bound, tend to be lifted to a height above the surface that is dependent on the aerosol radius, so that in steady state the variation of aerosol radius with height is well-defined. We develop an extension of Parker’s coronal flow theory to include the effect of aerosols carried along by the gas and use this to estimate the optical depth of such an atmosphere. For KBOs with CO evaporation from the surface and with radii in the range 245-334 km, line-of-site optical depths through the atmosphere can exceed one at heights of a few hundred kilometers above the surface. Such aerosol layers should be observable, and might be used to infer the flow proprieties of the escaping gas.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

On the dynamics of the jovian ionosphere and thermosphere.: IV. Ion-neutral coupling

We use the fully coupled, three-dimensional, global circulation Jovian Ionospheric Model (JIM) to calculate the coupling between ions in the jovian auroral ovals and the co-existing neutral atmosphere. The model shows that ions subject to drift motion around the auroral oval, as a result of the E×B coupling between a meridional, equatorward electric field and the jovian magnetic field, generate neutral winds in the planetary frame of reference. Unconstrained by the magnetic field, these neutral winds have a greater latitudinal extent than the corresponding ion drifts. Values of the coupling coefficient, k(h), are presented as a function of altitude and cross-auroral electric field strength, for different incoming electron fluxes and energies. The results show that, with ion velocities of several hundred metres per second to over 1 km s⁻¹, k(h) can attain values greater than 0.5 at the ion production peak. This parameter is key to calculating the effective conductivities required to model magnetosphere-ionosphere coupling correctly. The extent to which angular momentum (and therefore energy) is transported vertically in JIM is much more limited than earlier, one-dimensional, studies have predicted.