Semiperiodic variations in CO2 abundance on Venus

Photoelectric spectral scans of the P branch of the 8689 Å CO₂ band on Venus were made using the 107-inch coude scanner during seven observing periods in the past 2 years. The relative CO₂ line strength was determined for each scan, then normalized to remove the spatial variations leaving only temporal variations.The 4-day periodicity in the relative CO₂ line strength noted by Young et al. (1973) is not unique; we do confirm their 4-day periodicity in August 1973. Four other observing periods rule out a 4-day periodicity.A definite North-South asymmetry in the relative CO₂ line strength is noted during 1973, in most cases with the same periodicity present in both hemispheres. When the slit positions are referred to the equator of Venus, particularly near inferior conjunction, the large asymmetrics between the slit positions can be explained by a greater CO₂ line strength over the polar regions and weaker over the equatorial latitudes. The amplitude of variation of each position on the crescent is much greater near inferior conjunction either because we are sampling a smaller area on the planet or because the upper atmospheric abundance is more sensitive to the mechanism causing the variation in the smaller regions sampled at inferior conjunction.Simultaneous H₂O measurementsduring several of the observing runs indicate a lack of correlation in the relative CO₂ line strengths and the H₂O abundance.     

Observations of the phase variation of Venus CO2 equivalent widths

We present equivalent widths of Venus CO₂ scans of the P branch (P8–P32) of the 5ν₃ band at 8689 Å, the P16 line of the 5ν₃ band, and the P14 line of the ν₁ + 5ν₃ band at 7820 Å covering phase angles between 5°.1 and 170°. The equivalent widths reach a minimum at 10°, in agreement with a phase function with a backward lobe at 160° which is caused by a single internal reflection within the cloud particles. This is evidence that Venus cloud particles are composed of liquid droplets. Maximum equivalent widths are observed at ～60°, a value which is closer to the maximum of single-layer Mie scattering models than to that of two-layer models. At high phase angles we observe equivalent widths greater than those computed from homogeneous scattering models, indicating that at high altitudes the mixing ratio of scattering particles to CO₂ increases with depth. At all phase angles, particularly at large phase angles, the temporal and spatial variations in the observed equivalent widths confuse the phase variation.     

Venus: On the phase variation of CO2 line profiles

The shapes of Venus' CO₂ profiles are found to vary with solar phase angle. High-resolution spectra of the P16 and P14 lines in the 8689- and 7820-Å bands, respectively, are presented for phase angles ranging from 6 to 158°. The scattering mean free path at 80 mbar, approximately the effective pressure, is 1.7 km. Use of the van de Hulst similarity relations with simple, parametric scattering models is inadequare to separate effects due to the scattering phase function from those due to inhomogeneities in depth when one attempts to determine the atmospheric structure by fitting a family of such models over a wide range of phase angles.     

Transmission of CO2 in the atmosphere of Venus for the spectral region near 7 microns

The transmission in the 7-μm “window” opf Venus was calculated for a 7-layer model atmosphere. The synthetic spectra show that radiation from the layer 20–30 km above the surface would reach the top of the atmosphere between 6.2 and 7.0 μm if there were no absorption besides the isotopic CO₂ bands; for the 7.0- to 8.2-μm region, the radiating level would be located 40–50 km above the surface of Venus. The brightness temperature for the entire region is 430°K; for the above two regions it is 494 and 341°K, respectively.     

CO2 distribution on Mars

Ground-based observations of the CO₂ distribution on Mars were made this past opposition from Cerro Tololo Interamerican Observatory. Almost complete coverage of the Martian surface from 40°N to 60°S was obtained. Agreement with previous Kitt Peak observations is good, and confirmation of a pressure anomaly in the Tharsis region has been obtained. The ridge whose eastern slope is Syrtis Major stops at about 15°S, in agreement with the 1971 radar data. The Noachis-Hellas region south of Syrtis Major appears at about average altitude, indicating that the dust storm of 1971 was already active in that region as early as the end of August.     

Spatially-resolved high-resolution spectroscopy of Venus 1. Variations of CO2, CO, HF, and HCl at the cloud tops

Variations of the upper cloud boundary and the CO, HF, and HCl mixing ratios were observed using the CSHELL spectrograph at NASA IRTF. The observations were made in three sessions (October 2007, January 2009, and June 2009) at early morning and late afternoon on Venus in the latitude range of ±60°. CO₂ lines at 2.25 μm reveal variations of the cloud aerosol density (∼25%) and scale height near 65 km. The measured reflectivity of Venus at low latitudes is 0.7 at 2.25 μm and 0.028 at 3.66 μm, and the effective CO₂ column density is smaller at 3.66 μm than those at 2.25 μm by a factor of 4. This agrees with the almost conservative multiple scattering at 2.25 μm and single scattering in the almost black aerosol at 3.66 μm. The expected difference is just a factor of (1 − g)⁻¹ = 4, where g = 0.75 is the scattering asymmetry factor for Venus’ clouds. The observed CO mixing ratio is 52 ± 4 ppm near 08:00 and 40 ± 4 ppm near 16:30 at 68 km, and the higher ratio in the morning may be caused by extension of the CO morningside bulge to the cloud tops. The observed weak limb brightening in CO indicates an increase of the CO mixing ratio with altitude. HF is constant at 3.5 ± 0.2 ppb at 68 km in both morningside and afternoon observations and in the latitude range ±60°. Therefore the observations do not favor a bulge of HF, though HF is lighter than CO. Probably a source in the upper atmosphere facilitates the bulge formation. The recent measurements of HCl near 70 km are controversial (0.1 and 0.74 ppm) and require either a strong sink or a strong source of HCl in the clouds. The HCl lines of the (2-0) band are blended by the solar and telluric lines. Therefore we observed the P8 lines of the (1-0) band at 3.44 μm. These lines are spectrally clean and result in the HCl mixing ratio of 0.40 ± 0.03 ppm at 74 km. HCl does not vary with latitude within ±60°. Our observations support a uniformly mixed HCl throughout the Venus atmosphere.     

Venus phase function and forward scattering from H2SO4

Ground-based and spacecraft photometry covering phase angles from 2° to 179° has been acquired in wavelength bands from blue to near infrared. An unexpected brightness surge is seen in the B and V bands when the disk of Venus is less than 2% illuminated. This excess luminosity appears to be the result of forward scattering from droplets of H₂SO₄ (sulfuric acid) in the high atmosphere of Venus. The fully sunlit brightness of Venus, adjusted to a distance of one AU from the Sun and observer, was found to be V=−4.38, and the corresponding geometric albedo is 67%. The phase integral is 1.35 and the resulting spherical albedo is 90%. Comparison between our data and photometry obtained over the past 50 years indicates a bias in the older photoelectric results, however atmospheric abundance variations suggest that brightness changes may have occurred too.     

Release of N2, CH4, CO2, and H2O from surface ices on Enceladus

We vapor deposit at 20 K a mixture of gases with the specific Enceladus plume composition measured in situ by the Cassini INMS [Waite, J.H., Combi, M.R., Ip, W.H., Cravens, T.E., McNutt, R.L., Kasprzak, W., Yelle, R., Luhmann, J., Niemann, H., Gell, D., Magee, B., Fletcher, G., Lunine, J., Tseng, W.L., 2006. Science 311, 1419-1422] to form a mixed molecular ice. As the sample is slowly warmed, we monitor the escaping gas quantity and composition with a mass spectrometer. Pioneering studies [Schmitt, B., Klinger, J., 1987. Different trapping mechanisms of gases by water ice and their relevance for comet nuclei. In: Rolfe, E.J., Battrick, B. (Eds.), Diversity and Similarity of Comets. SP-278. ESA, Noordwijk, The Netherlands, pp. 613-619; Bar-Nun, A., Kleinfeld, I., Kochavi, E., 1988. Phys. Rev. B 38, 7749-7754; Bar-Nun, A., Kleinfeld, I., 1989. Icarus 80, 243-253] have shown that significant quantities of volatile gases can be trapped in a water ice matrix well above the temperature at which the pure volatile ice would sublime. For our Enceladus ice mixture, a composition of escaping gases similar to that detected by Cassini in the Enceladus plume can be generated by the sublimation of the H₂O:CO₂:CH₄:N₂ mixture at temperatures between 135 and 155 K, comparable to the high temperatures inferred from the CIRS measurements [Spencer, J.R., Pearl, J.C., Segura, M., Flasar, F.M., Mamoutkine, A., Romani, P., Buratti, B.J., Hendrix, A.R., Spilker, L.J., Lopes, R.M.C., 2006. Science 311, 1401-1405] of the Enceladus “tiger stripes.” This suggests that the gas escape phenomena that we measure in our experiments are an important process contributing to the gases emitted from Enceladus. A similar experiment for ice deposited at 70 K shows that both the processes of volatile trapping and release are temperature dependent over the temperature range relevant to Enceladus.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

Kinetics of CO2 production on venus

Consideration of theoretical limits and experimental data for the kinetics of the reaction quartz + calcite → wollastonite + CO₂ supports the concept of a shortterm quasiequilibrium state for the atmosphere of Venus. These data indicate that the time scale of this reaction and of any competing CO₂ producing reaction may be as short as several hundred years or less at the inferred Venus surface temperatures.     

Jupiter's hydrocarbon polar brightening: Discovery of 3-micron line emission from south polar CH4, C2H2, and C2H6

Jupiter exhibits bright H⁺₃ auroral arcs at 3-4 microns that cool the hot (>1000 K) ionosphere above the ∼¹⁰−7 bar level through the infrared bands of this trace constituent. Below the ¹⁰−7 bar level significant cooling proceeds through infrared active bands of CH₄, C₂H₂, and C₂H₆. We report the discovery of 3-micron line emission from these hydrocarbon species in spectra of the jovian south polar region obtained on April 18 and 20, 2006 (UT) with CGS4 on the United Kingdom Infrared Telescope. Estimated cooling rates through these molecules are 7.5×¹⁰−3, 1.4×¹⁰−3, and , respectively, for a total nearly half that of H⁺₃. We derive a temperature of 450 ± 50 K in the ¹⁰−7-¹⁰−5 bar region from the C₂H₂ lines.     

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.     

Sublimation kinetics of CO2 ice on Mars

Dynamic models of the martian polar caps are in abundance, but most rely on the assumption that the rate of sublimation of CO₂ ice can be calculated from heat transfer and lack experimental verification. We experimentally measured the sublimation rate of pure CO₂ ice under simulated martian conditions as a test of this assumption, developed a model based on our experimental results, and compared our model's predictions with observations from several martian missions (MRO, MGS, Viking). We show that sun irradiance is the primary control for the sublimation of CO₂ ice on the martian poles with the amount of radiation penetrating the surface being controlled by variations in the optical depth, ensuring the formation and sublimation of the seasonal cap. Our model confirmed by comparison of MGS-MOC and MRO-HiRISE images, separated by 2-3 martian years, shows that ∼0.4 m are currently being lost from the south perennial cap per martian year. At this rate, the ∼2.4-m-thick south CO₂ perennial cap will disappear in about 6-7 martian years, unless a short-scale climatic cycle alters this rate of retreat.     

High-resolution spectroscopy of Saturn at 3 microns: CH4, CH3D, C2H2, C2H6, PH3, clouds, and haze

We report observation and analysis of a high-resolution 2.87-3.54 μm spectrum of the southern temperate region of Saturn obtained with NIRSPEC at Keck II. The spectrum reveals absorption and emission lines of five molecular species as well as spectral features of haze particles. The ν₂+ν₃ band of CH₃D is detected in absorption between 2.87 and 2.92 μm; and we derived from it a mixing ratio approximately consistent with the Infrared Space Observatory result. The ν₃ band of C₂H₂ also is detected in absorption between 2.95 and 3.05 μm; analysis indicates a sudden drop in the C₂H₂ mixing ratio at 15 mbar (130 km above the 1 bar level), probably due to condensation in the low stratosphere. The presence of the ν₃+ν₉+ν₁₁ band of C₂H₆ near 3.07 μm, first reported by Bjoraker et al. [Bjoraker, G.L., Larson, H.P., Fink, U., 1981. Astrophys. J. 248, 856-862], is confirmed, and a C₂H₆ condensation altitude of 10 mbar (140 km) in the low stratosphere is determined. We assign weak emission lines within the 3.3 μm band of CH₄ to the ν₇ band of C₂H₆, and derive a mixing ratio of 9±4×¹⁰⁻⁶ for this species. Most of the C₂H₆ 3.3 μm line emission arises in the altitude range 460-620 km (at ∼μbar pressure levels), much higher than the 160-370 km range where the 12 μm thermal molecular line emission of this species arises. At 2.87-2.90 μm the major absorber is tropospheric PH₃. The cloud level determined here and at 3.22-3.54 is 390-460 mbar (∼30 km), somewhat higher than found by Kim and Geballe [Kim, S.J., Geballe, T.R., 2005. Icarus 179, 449-458] from analysis of a low resolution spectrum. A broad absorption feature at 2.96 μm, which might be due to NH₃ ice particles in saturnian clouds, is also present. The effect of a haze layer at about 125 km (∼12 mbar level) on the 3.20-3.54 μm spectrum, which was not apparent in the low resolution spectrum, is clearly evident in the high resolution data, and the spectral properties of the haze particles suggest that they are composed of hydrocarbons.     

Concatenation of HRSC colour and OMEGA data for the determination and 3D-parameterization of high-altitude CO2 clouds in the Martian atmosphere

We used Mars Express HRSC and OMEGA data to investigate mesospheric cloud features observed in the equatorial belt of Mars from December 2007 until early March 2008. This period corresponds to early northern spring of Martian year 29. The reflection peak at 4.26 μm in OMEGA data identifies the clouds as CO₂ ice clouds. HRSC observed the clouds together with OMEGA in five orbits. Cloud features are most prominent in the shortwave HRSC colour channels with wavelength centers at 440 and 530 nm, but rarely visible in all other channels. In the period of Ls 0-36°, OMEGA and HRSC together detected mesospheric CO₂ ice clouds in 40 orbits. They occur in a latitude belt of ±20° around the equator and at longitudes between 240°E (Tharsis) in the West and 30°E (Sinus Meridiani) in the East. The clouds were observed between 3 and 5 p.m. local time with mainly ripple-like to filamentary cloud forms. The viewing angles of the HRSC blue and green colour channels differ by 6.6° and the resulting parallax can be used to directly measure cloud heights by means of ray intersection. 17 HRSC data takes were found to exhibit clouds with heights from 66 to 83 km with an accuracy of 1-2 km. The pushbroom imaging technique also yields a time delay for the two observations in the order of 5-15 s close to periapsis, and therefore time-related cloud movements can be detected. A method was developed to determine the across-track cloud displacements, which can directly be translated to wind velocities. Zonal cloud movements could be measured in 13 cases and were oriented from East to West. Related wind speeds range between 60 and 93 m/s with an accuracy of 10-13 m/s.     

The microwave absorption of SO2 in the Venus atmosphere

Sulfur dioxide has a strong and complex rotational spectrum in the microwave and far infrared regions. The microwave absorption due to SO₂ in a CO₂ mixture is calculated for conditions applicable to the Venus atmosphere. It is shown that at the concentrations detected by Pioneer-Venus in situ measurements, SO₂ may be expected to contribute significantly to the microwave opacity of the Venus atmosphere. In particular, SO₂ might provide the major source of opacity in the atmospheric region immediately below the main sulfuric acid cloud deck. The spectrum is largely nonresonant at the pressures where SO₂ is expected to occur, however.     

Sulfur chemistry in the Venus mesosphere from SO2 and SO microwave spectra

First measurements of SO₂ and SO in the Venus mesosphere (70-100 km) are reported. This altitude range is distinctly above the ∼60-70 km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO₂, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO₂ and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO₂ and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO₂/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO₂ and SO at 85-100 km than at 70-85 km. The observed increase of SO₂ mixing ratio with altitude requires that the primary SO₂ source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO₂. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO + SO₂) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO₂.     

Warming the early earth—CO2 reconsidered

Despite a fainter Sun, the surface of the early Earth was mostly ice-free. Proposed solutions to this so-called “faint young Sun problem” have usually involved higher amounts of greenhouse gases than present in the modern-day atmosphere. However, geological evidence seemed to indicate that the atmospheric CO₂ concentrations during the Archaean and Proterozoic were far too low to keep the surface from freezing. With a radiative-convective model including new, updated thermal absorption coefficients, we found that the amount of CO₂ necessary to obtain 273 K at the surface is reduced up to an order of magnitude compared to previous studies. For the late Archaean and early Proterozoic period of the Earth, we calculate that CO₂ partial pressures of only about 2.9 mb are required to keep its surface from freezing which is compatible with the amount inferred from sediment studies. This conclusion was not significantly changed when we varied model parameters such as relative humidity or surface albedo, obtaining CO₂ partial pressures for the late Archaean between 1.5 and 5.5 mb. Thus, the contradiction between sediment data and model results disappears for the late Archaean and early proterozoic.     

Spatially-resolved high-resolution spectroscopy of Venus 2. Variations of HDO, OCS, and SO2 at the cloud tops

While CO, HCl, and HF, that were considered in the first part of this work, have distinct absorption lines in high-resolution spectra and were detected four decades ago, the lines of HDO, OCS, and SO₂ are either very weak or blended by the telluric lines and have not been observed previously by ground-based infrared spectroscopy at the Venus cloud tops. The H₂O abundance above the Venus clouds is typically below the detection limit of ground-based IR spectroscopy. However, the large D/H ratio on Venus facilitates observations of HDO. Converted to H₂O with D/H ≈ 200, our observations at 2722 cm⁻¹ in the Venus afternoon show a H₂O mixing ratio of ∼1.2 ppm at latitudes between ±40° increasing to ±60° by a factor of 2. The observations in the early morning reveal the H₂O mixing ratio that is almost constant at 2.9 ppm within latitudes of ±75°. The measured H₂O mixing ratios refer to 74 km. The observed increase in H₂O is explained by the lack of photochemical production of sulfuric acid in the night time. The recent observations at the P-branch of OCS at 4094 cm⁻¹ confirm our detection of OCS. Four distributions of OCS along the disk of Venus at various latitudes and local times have been retrieved. Both regular and irregular components are present in the variations of OCS. The observed OCS mixing ratio at 65 km varies from ∼0.3 to 9 ppb with the mean value of ∼3 ppb. The OCS scale height is retrieved from the observed limb darkening and varies from 1 to 4 km with a mean value of half the atmospheric scale height. SO₂ at the cloud tops has been detected for the first time by means of ground-based infrared spectroscopy. The SO₂ lines look irregular in the observed spectra at 2476 cm⁻¹. The SO₂ abundances are retrieved by fitting by synthetic spectra, and two methods have been applied to determine uncertainties and detection limits in this fitting. The retrieved mean SO₂ mixing ratio of 350 ± 50 ppb at 72 km favors a significant increase in SO₂ above the clouds since the period of 1980-1995 that was observed by the SOIR occultations at Venus Express. Scale heights of OCS and SO₂ may be similar, and the SO₂/OCS ratio is ∼500 and may be rather stable at 65-70 km under varying conditions on Venus.     

Martian glaciation and the flow of solid CO2

The flow law determined experimentally for solid CO₂ establishes that a hypothesis of glacial flow of CO₂ at the Martian poles is not physically unrealistic. Compression experiments carried out under 1 atm pressure and constant strain rate demonstrate that the strength of CO₂ near its sublimation point is considerably less than the strength of water ice near its melting point. The data fit a power law “creep” equation of the form

$\text{?}\text{?}\text{= (4 × 10}{}^6\text{) σ}{}^{3.9}\text{exp}\text{(}\text{?12 200}\text{RT}\text{)}$

, where ? is compressive strain rate (sec^?1), σ is compressive stress (bars), R is the gas constant in calories per mole, and T is absolute temperature. The exponent of σ of 3.9 contrasts with a value near 3.1 for water ice, and indicates that the strain rate is somewhat more sensitive to stress for CO₂ than for water. Likewise, the low activation energy for creep, 12 200 cal mole^?1, illustrates that CO₂ is not highly sensitive to temperature and is thus likely to flow over a broad range of temperatures below its melting point. Strength values for CO₂ are of the order of one-tenth to one-third the strength of ice under equivalent conditions.A plausible glacial model for the Martian polar caps can be constructed and is helpful in explaining the unique character of the polar regions. CO₂-rich layers deposited near the pole would have flowed outward laterally to relieve high internal shear stresses. The topography of the polar caps, the uniform layering of the layered deposits, and the general extent of the polar “sediments” could all be explained using this model. Flow of CO₂ rather than water ice greatly reduces the problems with Martian glaciation. Nevertheless, problems do remain, in particular the large amounts of CO₂ necessary, the need to increase vapor pressure and temperature with depth in the polar deposits, and the lack of good observational evidence of flor features. Within the limits of the present knowledge of surface conditions of Mars, CO₂ glaciation appears to be a realistic alternate working hypothesis for the origin of the polar features.