Comparison of PFS and TES observations of temperature and water vapor in the martian atmosphere

The interval from L_s = 330° in Mars Year (MY) 26 until L_s = 84° in MY 27 has been used to compare and validate measurements from the Mars Global Surveyor Thermal Emission Spectrometer (TES) and the Mars Express Planetary Fourier Spectrometer (PFS). We studied differences between atmospheric temperatures observed by the two instruments. The best agreement between atmospheric temperatures was found at 50 Pa between 40°S and 40°N latitude, where differences were within ±5 K. For other atmospheric levels, differences as large as ∼25 K were observed between the two instruments at some locations. The largest temperature differences occurred mainly over the Hellas Planitia, Argyre Planitia, Tharsis and Valles Marineris regions.On this basis we report on the variability of the martian atmosphere during the 5.5 martian years of Mars climatology obtained by combining the two data sets from TES and PFS. Atmospheric temperatures at 50 Pa responded to the global-scale dust storms of MY 25 and in MY 28 raising temperatures from ∼220 K to ∼250 K during the daytime. An atmospheric temperature of ∼140 K at 50 Pa was observed poleward of 70°N during northern winter and poleward of 60°S during southern winter each year in both the PFS and TES results. Water vapor observed by the two spectrometers showed consistent seasonal and latitudinal variations.     

Limits on the trapping of atmospheric CH4 in martian polar ice analogs

Recent detection of methane (CH₄) on Mars has generated interest in possible biological or geological sources, but the factors responsible for the reported variability are not understood. Here we explore one potential sink that might affect the seasonal cycling of CH₄ on Mars - trapping in ices deposited on the surface. Our apparatus consisted of a high-vacuum chamber in which three different Mars ice analogs (water, carbon dioxide, and carbon dioxide clathrate hydrates) were deposited in the presence of CH₄ gas. The ices were monitored for spectroscopic evidence of CH₄ trapping using transmission Fourier-Transform Infrared (FT-IR) spectroscopy, and during subsequent sublimation of the ice films the vapor composition was measured using mass spectrometry (MS). Trapping of CH₄ in water ice was confirmed at deposition temperatures <100 K which is consistent with previous work, thus validating the experimental methods. However, no trapping of CH₄ was observed in the ice analogs studied at warmer temperatures (140 K for H₂O and CO₂ clathrate, 90 K for CO₂ snow) with approximately 10 mTorr CH₄ in the chamber. From experimental detection limits these results provide an upper limit of 0.02 for the atmosphere/ice trapping ratio of CH₄. If it is assumed that the trapping mechanism is linear with CH₄ partial pressure and can be extrapolated to Mars, this upper limit would indicate that less than 1% is expected to be trapped from the largest reported CH₄ plume, and therefore does not represent a significant sink for CH₄.     

Extension of atmospheric dust loading to high altitudes during the 2001 Mars dust storm: MGS TES limb observations

Mars Global Surveyor (MGS) visible (solarband bolometer) and thermal infrared (IR) spectral limb observations from the Thermal Emission Spectrometer (TES) support quantitative profile retrievals for dust opacity and particle sizes during the 2001 global dust event on Mars. The current analysis considers the behavior of dust lifted to altitudes above 30 km during the course of this storm; in terms of dust vertical mixing, particle sizes, and global distribution. TES global maps of visible (solarband) limb brightness at 60 km altitude indicate a global-scale, seasonally evolving (over 190-240° solar longitudes, L_S) longitudinal corridor of vertically extended dust loading (which may be associated with a retrograde propagating, wavenumber 1 Rossby wave). Spherical radiative transfer analysis of selected limb profiles for TES visible and thermal IR radiances provide quantitative vertical profiles of dust opacity, indicating regional conditions of altitude-increasing dust mixing ratios. Observed infrared spectral dependences and visible-to-infrared opacity ratios of dust scattering over 30-60 km altitudes indicate particle sizes characteristic of lower altitudes (cross-section weighted effective radius, ), during conditions of significant dust transport to these altitudes. Conditions of reduced dust loading at 30-60 km altitudes present smaller dust particle sizes . These observations suggest rapid meridional transport at 30-80 km altitudes, with substantial longitudinal variation, of dust lifted to these altitudes over southern hemisphere atmospheric regions characterized by extraordinary (m/s) vertical advection velocities. By L_S=230° dust loading above 50 km altitudes decreased markedly at southern latitudes, with a high altitude (60-80 km) haze of fine (likely) water ice particles appearing over 10°S-40°N latitudes.     

A sensitive search for SO2 in the martian atmosphere: Implications for seepage and origin of methane

Mars was observed near the peak of the strongest SO₂ band at 1364-1373 cm⁻¹ with resolving power of 77,000 using the Texas Echelon Cross Echelle Spectrograph on the NASA Infrared Telescope Facility. The observation covered the Tharsis volcano region which may be preferable to search for SO₂. The spectrum shows absorption lines of three CO₂ isotopomers and three H₂O isotopomers. The water vapor abundance derived from the HDO lines assuming D/H = 5.5 times the terrestrial value is 12±1.0 pr. μm, in agreement with the simultaneous MGS/TES observations of 14 pr. μm at the latitudes (50° S to 10° N) of our observation. Summing of spectral intervals at the expected positions of sixteen SO₂ lines puts a 2σ upper limit on SO₂ of 1 ppb. SO₂ may be emitted into the martian atmosphere by seepage and is removed by three-body reactions with OH and O. The SO₂ lifetime, 2 years, is longer than the global mixing time 0.5 year, so SO₂ should be rather uniformly distributed across Mars. Seepage of SO₂ is less than 15,000 tons per year on Mars which is smaller than the volcanic production of SO₂ on the Earth by a factor of 700. Because CH₄/SO₂ is typically 10⁻⁴-10⁻³ in volcanic gases on the Earth, our results show seepage is unlikely to be the source of the recently discovered methane on Mars and therefore strengthen its biogenic origin.     

Is there methane on Mars?

There have been several reports of methane on Mars at the 10-60 ppbv level. Most suggest that methane is both seasonally and latitudinally variable. Here we review why variable methane on Mars is physically and chemically implausible, and then we critically review the published reports. There is no known mechanism for destroying methane chemically on Mars. But if there is one, methane oxidation would deplete the O₂ in Mars’s atmosphere in less than 10,000 years unless balanced by an equally large unknown source of oxidizing power. Physical sequestration does not raise these questions, but adsorption in the regolith or condensation in clathrates ignore competition for adsorption sites or are inconsistent with clathrate stability, respectively. Furthermore, any mechanism that relies on methane’s van der Waals’ attraction is inconsistent with the continued presence of Xe in the atmosphere at the 60 ppbv level. We then use the HITRAN database and transmission calculations to identify and characterize the absorption lines that would be present on Earth or Mars at the wavelengths of the published observations. These reveal strong competing telluric absorption that is most problematic at just those wavelengths where methane’s signature seems most clearly seen from Earth. The competing telluric lines must be removed with models. The best case for martian methane was made for the ¹²CH₄ν₃ R0 and R1 lines seen in blueshift when Mars was approaching Earth in early 2003 (Mumma, M.J., Villanueva, G.L., Novak, R.E., Hewagama, T., Bonev, B.P., DiSanti, M.A., Mandell, A.M., Smith, M.D. [2009]. Science 323, 1041-1045). For these the Doppler shift moves the two martian lines into near coincidence with telluric ¹³CH₄ν₃ R1 and R2 lines that are 10-50× stronger than the inferred martian lines. By contrast, the ¹²CH₄ν₃ R0 and R1 lines when observed in redshift do not contend with telluric ¹³CH₄. For these lines, Mumma et al.’s observations and analyses are consistent with an upper limit on the order of 3 ppbv.     

Investigation of water vapor on Mars with PFS/SW of Mars Express

New insight into the seasonal, diurnal and spatial distribution of water vapor on Mars has been obtained from analyzing the spectra of the short-wavelength channel (SW) of the Planetary Fourier Spectrometer (PFS) onboard Mars Express. The processed dataset, recorded between January 2004 and April 2005, covers the seasons from LS=331° of Mars Year 26 to LS=196° of the following year. In this period the mean column density around vernal equinox was 8.2 pr. μm. The maximum values during northern summer were about 65 pr. μm, located around 75° N latitude with a longitudinally inhomogeneous distribution. Regarding the atmospheric transport, the majority of polar water vapor remains in the north polar region while only about a quarter is transported southward. Geographically there are two water vapor maxima visible, over Arabia Terra and the Tharsis plateau, that are most likely caused both by atmosphere-ground interaction and by atmospheric circulation. A comparison with other instruments generally shows a good agreement, only the SPICAM results are systematically lower. Compared to the results from the PFS long-wavelength channel the results of this work are slightly higher. A strong discrepancy is visible northward of about 50° N during the northern summer that is possibly explained by a non-uniform vertical H₂O mixing. In particular, a confinement of the water to the lower few kilometers yields a much better agreement between the retrieved column densities of the two PFS channels.     

Stability of methane clathrate hydrates under pressure: Influence on outgassing processes of methane on Titan

We have conducted high-pressure experiments in the H₂O-CH₄ and H₂O-CH₄-NH₃ systems in order to investigate the stability of methane clathrate hydrates, with an optical sapphire-anvil cell coupled to a Raman spectrometer for sample characterization. The results obtained confirm that three factors determine the stability of methane clathrate hydrates: (1) the bulk methane content of the samples; (2) the presence of additional gas compounds such as nitrogen; (3) the concentration of ammonia in the aqueous solution. We show that ammonia has a strong effect on the stability of methane clathrates. For example, a 10 wt.% NH₃ solution decreases the dissociation temperature of methane clathrates by 14-25 K at pressures above 5 MPa. Then, we apply these new results to Titan’s conditions. Dissociation of methane clathrate hydrates and subsequent outgassing can only occur in Titan’s icy crust, in presence of locally large amounts of ammonia and in a warm context. We propose a model of cryomagma chamber within the crust that provides the required conditions for methane outgassing: emplacement of an ice plume triggers the melting (if solid) or heating (if liquid) of large ammonia-water pockets trapped at shallow depth, and the generated cryomagmas dissociate surrounding methane clathrate hydrates. We show that this model may allow for the outgassing of significant amounts of methane, which would be sufficient to maintain the presence of methane in Titan’s atmosphere for several tens of thousands of years after a large cryovolcanic event.     

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.     

Incorporation of argon, krypton and xenon into clathrates on Mars

Calculations of the trapping of heavy noble gases within multiple guest clathrates under Mars-like conditions show that a substantial fraction of the martian Xe, perhaps even the vast majority, could be in clathrates. In addition, the Xe/Kr ratio in the clathrates would probably be much higher than in the atmosphere, so the formation or dissociation of a relatively small amount of clathrate could measurably change the atmospheric ratio. Relatively crude (factor of 2) measurements of the seasonal variability in that ratio by in situ spacecraft would be sensitive to ∼10% of the seasonal atmospheric CO₂ variability being a result of clathrates, rather than pure CO₂ frost. In addition, sequestration of Xe in clathrates remains a viable mechanism for explaining the variable Xe/Kr ratios seen in different suites of martian meteorites.     

The near-IR spectrum of Titan modeled with an improved methane line list

We have obtained spatially resolved spectra of Titan in the near-infrared J, H and K bands at a resolving power of ∼5000 using the near-infrared integral field spectrometer (NIFS) on the Gemini North 8 m telescope. Using recent data from the Cassini/Huygens mission on the atmospheric composition and surface and aerosol properties, we develop a multiple-scattering radiative transfer model for the Titan atmosphere. The Titan spectrum at these wavelengths is dominated by absorption due to methane with a series of strong absorption band systems separated by window regions where the surface of Titan can be seen. We use a line-by-line approach to derive the methane absorption coefficients. The methane spectrum is only accurately represented in standard line lists down to ∼2.1 μm. However, by making use of recent laboratory data and modeling of the methane spectrum we are able to construct a new line list that can be used down to 1.3 μm. The new line list allows us to generate spectra that are a good match to the observations at all wavelengths longer than 1.3 μm and allow us to model regions, such as the 1.55 μm window that could not be studied usefully with previous line lists such as HITRAN 2008. We point out the importance of the far-wing line shape of strong methane lines in determining the shape of the methane windows. Line shapes with Lorentzian, and sub-Lorentzian regions are needed to match the shape of the windows, but different shape parameters are needed for the 1.55 μm and 2 μm windows. After the methane lines are modeled our observations are sensitive to additional absorptions, and we use the data in the 1.55 μm region to determine a D/H ratio of 1.77 ± 0.20 × 10⁻⁴, and a CO mixing ratio of 50 ± 11 ppmv. In the 2 μm window we detect absorption features that can be identified with the ν₅ + 3ν₆ and 2ν₃ + 2ν₆ bands of CH₃D.     

Annual survey of water vapor behavior from the OMEGA mapping spectrometer onboard Mars Express

We present here the annual behavior of atmospheric water vapor on Mars, as observed by the OMEGA spectrometer on board Mars Express during its first martian year. We consider all the different features of the cycle of water vapor: temporal evolution, both at a seasonal and at a diurnal scale; longitudinal distribution; and the vertical profile, through the variations in the saturation height. We put our results into the context of the current knowledge on the water cycle through a systematic comparison with the already published datasets. The seasonal behavior is in very good agreement with past and simultaneous retrievals both qualitatively and quantitatively, within the uncertainties. The average water vapor abundance during the year is ∼10 pr. μm, with an imbalance between northern and southern hemisphere, in favor of the first. The maximum of activity, up to 60 pr. μm, occurs at high northern latitudes during local summer and shows the dominance of the northern polar cap within the driving processes of the water cycle. A corresponding maximum at southern polar latitudes during the local summer is present, but less structured and intense. It reaches ∼25 pr. μm at its peak. Global circulation has some influence in shaping the water cycle, but it is less prominent than the results from previous instruments suggest. No significant correlation between water vapor column density and local hour is detected. We can constrain the amount of water vapor exchanged between the surface and the atmosphere to few pr. μm. This is consistent with recent results by OMEGA and PFS-LW. The action of the regolith layer on the global water cycle seems to be minor, but it cannot be precisely constrained. The distribution of water vapor on the planet, after removing the topography, shows the already known two-maxima system, over Tharsis and Arabia Terra. However, the Arabia Terra increase is quite fragmented compared with previous observations. A deep zone of minimum separates the two regions. The saturation height of water vapor is mainly governed by the variations of insolation during the year. It is confined within 5-15 km from the surface at aphelion, while in the perihelion season it stretches up to 55 km of altitude.     

Water vapor variability in the north polar region of Mars from Viking MAWD and MGS TES datasets

Atmospheric water vapor abundances in Mars’ north polar region (NPR, from 60° to 90°N) are mapped as function of latitude and longitude for spring and summer seasons, and their spatial, seasonal, and interannual variability is discussed. Water vapor data are from Mars Global Surveyor (MGS) Thermal Emission Spectrometer (TES) and the Viking Orbiter (VO) Mars Atmospheric Water Detector (MAWD). The data cover three complete northern spring-summer seasons in 1977-1978, 2000-2001 and 2002-2003, and shorter periods of spring-summer seasons during 1975, 1999 and 2004. Long term interannual variability in the averaged NPR abundances may exist, with Viking MAWD observations showing twice as much water vapor during summer as the MGS TES observations more than 10 martian years (MY) later. While the averaged abundances are very similar in TES observations for the same season in different years, the spatial distributions in the early summer season do vary significantly year over year. Spatial and temporal variabilities increase between L_s ∼ 80-140°, which may be related to vapor sublimation from the North Polar Residual Cap (NPRC), or to changes in circulation. Spatial variability is observed on scales of ∼100 km and temporal variability is observed on scales of <10 sols during summer. During late spring the TES water vapor spatial distribution is seen to correlate with the low topography/low albedo region of northern Acidalia Planitia (270-360°E), and with the dust spatial distribution across the NPR during late spring-early summer. Non-uniform vertical distribution of water vapor, a regolith source or atmospheric circulation ‘pooling’ of water vapor from the NPRC into the topographic depression may be behind the correlation with low topography/low albedo. Sublimation winds carrying water vapor off the NPRC and lifting surface dust in the areas surrounding the NPRC may explain the correlation between the water vapor and dust spatial distributions. Correlation between water vapor and dust in MAWD data are only observed over low topography/low albedo area. Maximum water vapor abundances are observed at L_s = 105-115° and outside of the NPRC at 75-80°N; the TES data, however, do not extend over the NPRC and thus, this conclusion may be biased. Some water vapor appears to be released in plumes or ‘outbursts’ in the MAWD and TES datasets during late spring and early summer. We propose that the sublimation rate of ice varies across the NPRC with varying surface winds, giving rise to the observed ‘outbursts’ at some seasons.     

MGS TES observations of the water vapor above the seasonal and perennial ice caps during northern spring and summer

We report on new retrievals of water vapor column abundances from the Mars Global Surveyor (MGS) Thermal Emission Spectrometer (TES) data. The new retrievals are from the TES nadir data taken above the ‘cold’ surface areas in the North polar region (T_surf < 220 K, including seasonal frost and permanent ice cap) during spring and summer seasons, where retrievals were not performed initially. Retrievals are possible (with some modifications to the original algorithm) over cold surfaces overlaid by sufficiently warm atmosphere. The retrieved water vapor column abundances are compared to the column abundances observed by other spacecrafts in the Northern polar region during spring and summer and good agreement is found. We detect an annulus of water vapor growing above the edge of the retreating seasonal cap during spring. The formation of the vapor annulus is consistent with the previously proposed mechanism for water cycling in the polar region, according to which vapor released by frost sublimation during spring re-condenses on the retreating seasonal CO₂ cap. The source of the vapor in the vapor annulus, according to this model, is the water frost on the surface of the CO₂ at the retreating edge of the cap and the frost on the ground that is exposed by the retreating cap. Small contribution from regolith sources is possible too, but cannot be quantified based on the TES vapor data alone. Water vapor annulus exhibits interannual variability, which we attribute to variations in the atmospheric temperature. We propose that during spring and summer the water ice sublimation is retarded by high relative humidity of the local atmosphere, and that higher atmospheric temperatures lead to higher vapor column abundances by increasing the water holding capacity of the atmosphere. Since the atmospheric temperatures are strongly influenced by the atmospheric dust content, local dust storms may be controlling the release of vapor into the polar atmosphere. Water vapor abundances above the residual polar cap also exhibit noticeable interannual variability. In some years abundances above the cap are lower than the abundances outside of the cap, consistent with previous observations, while in the other years the abundances above the cap are higher or similar to abundances outside of the cap. We speculate that the differences may be due to weaker off-cap transport in the latter case, keeping more vapor closer to the source at the surface of the residual cap. Despite the large observed variability in water vapor column abundances in the Northern polar region during spring and summer, the latitudinal distribution of the vapor mass in the atmosphere is very similar during the summer season. If the variability in vapor abundances is caused by the variability of vapor sources across the residual cap then this would mean that they annually contribute relatively little vapor mass to significantly affect the vapor mass budget. Alternatively this may suggest that the vapor variability is caused by the variability of the polar atmospheric circulation. The new water vapor retrievals should be useful in tuning the Global Circulation Models of the martian water cycle.     

Variability of the methane trapping in martian subsurface clathrate hydrates

Recent observations have evidenced traces of methane (CH₄) heterogeneously distributed in the martian atmosphere. However, because the lifetime of CH₄ in the atmosphere of Mars is estimated to be around 300-600 years on the basis of photochemistry, its release from a subsurface reservoir or an active primary source of methane have been invoked in the recent literature. Among the existing scenarios, it has been proposed that clathrate hydrates located in the near subsurface of Mars could be at the origin of the small quantities of the detected CH₄. Here, we accurately determine the composition of these clathrate hydrates, as a function of temperature and gas phase composition, by using a hybrid statistical thermodynamic model based on experimental data. Compared to the other recent works, our model allows us to calculate the composition of clathrate hydrates formed from a more plausible composition of the martian atmosphere by considering its main compounds, i.e. carbon dioxide, nitrogen and argon, together with methane. Besides, because there is no low temperature restriction in our model, we are able to determine the composition of clathrate hydrates formed at temperatures corresponding to the extreme ones measured in the polar caps. Our results show that methane enriched clathrate hydrates could be stable in the subsurface of Mars only if a primitive CH₄-rich atmosphere has existed or if a subsurface source of CH₄ has been (or is still) present.     

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.     

Interannual variability in TES atmospheric observations of Mars during 1999-2003

We use infrared spectra returned by the Mars Global Surveyor Thermal Emission Spectrometer (TES) to retrieve atmospheric and surface temperature, dust and water ice aerosol optical depth, and water vapor column abundance. The data presented here span more than two martian years (Mars Year 24, L_s=104°, 1 March 1999 to Mars Year 26, L_s=180°, 4 May 2003). We present an overview of the seasonal (L_s), latitudinal, and longitudinal dependence of atmospheric quantities during this period, as well as an initial assessment of the interannual variability in the current martian climate. We find that the perihelion season (L_s=180°-360°) is relatively warm, dusty, free of water ice clouds, and shows a relatively high degree of interannual variability in dust optical depth and atmospheric temperature. On the other hand, the aphelion season (L_s=0°-180°) is relatively cool, cloudy, free of dust, and shows a low degree of interannual variability. Water vapor abundance shows a moderate amount of interannual variability at all seasons, but the most in the perihelion season. Much of the small amount of interannual variability that is observed in the aphelion season appears to be caused by perihelion-season planet-encircling dust storms. These dust storms increase albedo through deposition of bright dust on the surface causing cooler daytime surface and atmospheric temperatures well after dust optical depth returns to prestorm values.     

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.     

Detection of methane in the martian atmosphere: evidence for life?

Using the Fourier Transform Spectrometer at the Canada-France-Hawaii Telescope, we observed a spectrum of Mars at the P-branch of the strongest CH₄ band at 3.3 μm with resolving power of 180,000 for the apodized spectrum. Summing up the spectral intervals at the expected positions of the 15 strongest Doppler-shifted martian lines, we detected the absorption by martian methane at a 3.7 sigma level which is exactly centered in the summed spectrum. The observed CH₄ mixing ratio is 10±3 ppb. Total photochemical loss of CH₄ in the martian atmosphere is equal to , the CH₄ lifetime is 340 years and methane should be uniformly mixed in the atmosphere. Heterogeneous loss of atmospheric methane is probably negligible, while the sink of CH₄ during its diffusion through the regolith may be significant. There are no processes of CH₄ formation in the atmosphere, so the photochemical loss must therefore be balanced by abiogenic and biogenic sources. Outgassing from Mars is weak, the latest volcanism is at least 10 million years old, and thermal emission imaging from the Mars Odyssey orbiter does not reveal any hot spots on Mars. Hydrothermal systems can hardly be warmer than the room temperature at which production of methane is very low in terrestrial waters. Therefore a significant production of hydrothermal and magmatic methane is not very likely on Mars. The calculated average production of CH₄ by cometary impacts is 2% of the methane loss. Production of methane by meteorites and interplanetary dust does not exceed 4% of the methane loss. Methane cannot originate from an extinct biosphere, as in the case of “natural gas” on Earth, given the exceedingly low limits on organic matter set by the Viking landers and the dry recent history which has been extremely hostile to the macroscopic life needed to generate the gas. Therefore, methanogenesis by living subterranean organisms is a plausible explanation for this discovery. Our estimates of the biomass and its production using the measured CH₄ abundance show that the martian biota may be extremely scarce and Mars may be generally sterile except for some oases.     

The haze and methane distributions on Neptune from HST-STIS spectroscopy

We analyzed a data cube of Neptune acquired with the Hubble STIS spectrograph on August 3, 2003. The data covered the full afternoon hemisphere at 0.1 arcsec spatial resolution between 300 and 1000 nm wavelength at 1 nm resolution. Navigation was accurate to 0.004 arcsec and 0.05 nm. We constrained the vertical aerosol structure with radiative transfer calculations. Ultraviolet data confirmed the presence of a stratospheric haze of optical depth 0.04 at 370 nm wavelength. Bright, discrete clouds, most abundant near latitudes −40° and 30°, had their top near the tropopause. They covered 1.7% of the observed disk if they were optically thick. The methane abundance above the cloud tops was 0.0026 and 0.0017 km-am for southern and northern clouds, respectively, identical to earlier observations by Sromovsky et al. (Sromovsky, L.A., Fry, P.M., Dowling, T.E., Baines, K.H., Limaye, S.S., [2001b]. Icarus 149, 459-488). Aside from these clouds, the upper troposphere was essentially clear. Below the 1.4-bar layer, a vertically uniform haze extended at least down to 10 bars with optical depth of 0.10-0.16/bar, depending on the latitude. Haze particles were bright at wavelengths above 600 nm, but darkened toward the ultraviolet, at the equator more so than at mid and high latitudes. A dark band near −60° latitude was caused by a 0.01 decrease of the single scattering albedo in the visible, which was close to unity. A comparison of methane and hydrogen absorptions contradicted the current view that methane is uniformly mixed in latitude and altitude below the ∼1.5-bar layer. The 0.04 ± 0.01 methane mixing ratio is only uniform at low latitudes. At high southern latitudes, it is depressed roughly between the 1.2 and 3.3-bar layers compared to low-latitude values. The maximum depression factor is ∼2.7 at 1.8 bars. We present models with 2° latitude sampling across the full sunlit globe that fit the observed reflectivities to 2.8% rms.