Titan's 5 micrometers spectral window: carbon monoxide and the albedo of the surface

We have measured the spectrum of Titan near 5 micrometers and have found it to be dominated by absorption from the carbon monoxide 1-0 vibration-rotation band. The position of the band edge allows us to constrain the abundance of CO in the atmosphere and/or the location of the reflecting layer in the atmosphere. In the most likely case, 5 micrometers radiation is reflected from the surface and the mole fraction of CO in the atmosphere is qCO=10(+10/-5) ppm, significantly lower than previous estimates for tropospheric CO. The albedo of the reflecting layer is approximately 0.07(+0.02/-0.01) in the 5 micrometers continuum outside the CO band. The 5 micrometers albedo is consistent with a surface of mixed ice and silicates similar to the icy Galilean satellites. Organic solids formed in simulated Titan conditions can also produce similar albedos at 5 micrometers.     

Observations of CO in the atmosphere of Mars with PFS onboard Mars Express

We have analyzed spectra of CO recorded with the instrument PFS onboard Mars Express in the (1-0) band. The dataset we used ranges in time from January until June 2004 (L_S=331^°.17 until L_S=51^°.61; end of Mars Year 26, beginning of Mars Year 27). The aim of this work was to determine the amplitude of the CO mixing ratio departures from the mean globally averaged value currently admitted (8±3×10^-4) [Kaplan, L.D., Connes, J., Connes, P., 1969. Carbon monoxide in the martian atmosphere. Astron. J. 157, L187-L192] as a function of season, local time and location on the planet. We therefore processed the data from 90 calibrated orbits. The globally averaged CO mixing ratio value we derive from our dataset, 11.1×10^-4, is compatible with the range found by Kaplan et al. [1969. Carbon monoxide in the martian atmosphere. Astron. J. 157, L187-L192], although somewhat higher than the “standard” value. However, the CO mixing ratio we retrieve exhibits large variations (roughly between 3×10^-4 and 18×10^-4). Such relative variations have been used on a statistical basis to derive main trends as a function of latitude for three L_S ranges: 331-360^°, 0-30^° and 30-52^°. For the first L_S range, we seem to have an enhancement of the CO mixing ratio towards the northern latitudes, probably linked to the CO₂ condensation in winter on the north polar cap. The situation for the two other L_S ranges is not so clear, mainly as we lack data on the southern hemisphere. We roughly agree with the work of Krasnopolsky [2007. Long-term spectroscopic observations of Mars using IRTF/CSHELL: mapping of O2 dayglow, CO and search for CH4. Icarus 190, 93-102] for L_S=331-360^°, thus confirming the effect of seasonal condensation of CO₂ on the north polar cap, but we have no agreement for other seasons.     

Mechanistic studies on the decomposition of carbon suboxide in a cometary ice analog

A cometary ice analog sample consisting primarily of carbon suboxide ice (C₃O₂) was produced from the irradiation of its precursor, carbon monoxide. This carbon suboxide sample was subjected to irradiation with energetic electrons at 10 K to simulate the interaction of carbon suboxide-rich cometary analog ices with ionizing radiation. The destruction of carbon suboxide as well as the production of the primary degradation products, dicarbon monoxide (C₂O), and carbon monoxide (CO), were monitored quantitatively by infrared spectroscopy in situ; the gas phase was simultaneously sampled via quadrupole mass spectrometry. A kinetic model was produced to help explain the decomposition kinetics of carbon suboxide in cometary ices and to infer the underlying reaction mechanisms.     

Carbon monoxide fluorescence from Titan's atmosphere

We report on the discovery of emissions due to carbon monoxide from Titan's atmosphere, from mid-infrared observations with the ISAAC spectrometer at the Very Large Telescope and covering the 4.50-4.85 μm range. We detected about 45 emission lines coinciding with CO ro-vibrational lines, including CO(1-0) (P18 to R11) and CO(2-1) (P11 to R11). We show that these emissions cannot be generated thermally but occur in non-LTE conditions, due to radiative de-excitation from the v=1 and v=2 CO levels after excitation at 4.7 and 2.3 μm by solar radiation. A complete fluorescence model is then developed, allowing to compute the state populations of the two most abundant CO isotopes and N₂(1). It includes absorption by CO and CH₄, and vibrational-thermal and vibrational-vibrational collisional exchanges with CO, N₂, CH₄, and H₂. Emerging radiances at the top of the atmosphere are evaluated with a line-by-line code and compared to observations. Contribution functions show that the CO emissions sound Titan's stratosphere: while the (1-0) lines generally probe two layers, located respectively at 100-250 km and 300-550 km, the (2-1) lines are sensitive to the intermediate layer at 150-300 km. A sensitivity study is performed to establish the effect of the main model parameters (temperature profile, collisional scenario, and CO stratospheric abundance) on the results. Models reproduce the essential structure of the observed emissions. The (1-0) fundamental band is generally well fit with a nominal CO mixing ratio of 32 ppm—as inferred in the troposphere from observations at 4.80-5.10 μm (Lellouch et al., 2003, Icarus 162, 126-143). However, this band is only weakly dependent on the CO abundance, and given temperature and collisional scenario uncertainties, it constrains the CO stratospheric mixing ratio only to within a factor of ∼3. In addition, the nominal model with 32 ppm CO underestimates the first hot (2-1) transition by approximately a factor of 2. This discrepancy can be resolved by a combined adjustment of collisional rates and an increased CO stratospheric ratio of 60 ppm, consistent with the determination of Gurwell and Muhleman (2000, Icarus 145, 653-656). In contrast, the CO vertical profile suggested by Hidayat et al. (1998, Icarus 133, 109-133), strongly depleted above 200 km, cannot match the data for any realistic collisional scenario, and is therefore not supported by our results.     

Observations of CO in the stratosphere of Venus via its J = 0 → 1 rotational transition

We have observed carbon monoxide in the stratosphere of Venus at phase angles of 180 and 120° via the J = 0 → 1 rotational transition at 115.2712 GHz. The mixing ratio profile of CO has been obtained by fitting the theoretical spectrum produced by a small number of layers with constant CO mixing ratio to the line profile, and the results suggest that the CO mixing ratio below the 1-mb level increased by at least a factor of 10 between 180 and 120° phase angles. The depletion of CO on the nightside of the planet was not anticipated and may require either a new loss mechanism for CO which can operate without sunlight or an increase in the amount of vertical mixing on the nightside.     

Observations of water vapour and carbon monoxide in the Martian atmosphere with the SWC of PFS/MEX

In the history of Mars exploration its atmosphere and planetary climatology aroused particular interest. In the study of the minor gases abundance in the Martian atmosphere, water vapour became especially important, both because it is the most variable trace gas, and because it is involved in several processes characterizing the planetary atmosphere. The water vapour photolysis regulates the Martian atmosphere photochemistry, and so it is strictly related to carbon monoxide. The CO study is very important for the so-called “atmosphere stability problem”, solved by the theoretical modelling involving photochemical reactions in which the H₂O and the CO gases are main characters.The Planetary Fourier Spectrometer (PFS) on board the ESA Mars Express (MEX) mission can probe the Mars atmosphere in the infrared spectral range between 200 and 2000 cm^?1 (5–50 μm) with the Long Wavelength Channel (LWC) and between 1700 and 8000 cm^?1 (1.2–5.8 μm) with the Short Wavelength Channel (SWC). Although there are several H₂O and CO absorption bands in the spectral range covered by PFS, we used the 3845 cm^?1 (2.6 μm) and the 4235 cm^?1 (2.36 μm) bands for the analysis of water vapour and carbon monoxide, respectively, because these ranges are less affected by instrumental problems than the other ones. The gaseous concentrations are retrieved by using an algorithm developed for this purpose.The PFS/SW dataset used in this work covers more than two and a half Martian years from Ls=62° of MY 27 (orbit 634) to Ls=203° of MY 29 (orbit 6537). We measured a mean column density of water vapour of about 9.6 pr. μm and a mean mixing ratio of carbon monoxide of about 990 ppm, but with strong seasonal variations at high latitudes. The seasonal water vapour map reproduces very well the known seasonal water cycle. In the northern summer, water vapour and CO show a good anticorrelation most of the time. This behaviour is due to the carbon dioxide and water sublimation from the north polar ice cap, which dilutes non-condensable species including carbon monoxide. An analogous process takes place during the winter polar cap, but in this case the condensation of carbon dioxide and water vapour causes an increase of the concentration of non-condensable species. Finally, the results show the seasonal variation of the carbon monoxide mixing ratio with the surface pressure.     

CO adsorption and the optical properties of interstellar grains

Laboratory data on the spectra of CO adsorbed on small MgO particles show that CO absorption leads to a weakening of the 220 nm band together with a shift of this band to shorter wavelengths. CO adsorption also results in the formation of a cyclic CO carbon ion that absorbs at 2.15 m^–1. It is shown that this band provides a close match to a major component of the very broad structure seen in interstellar extinction at the same energy. Effects of CO adsorption on the 220 nm band and VUV extinction are discussed in light of recent observational data on stars with peculiar extinction curves.     

Temperature and pressure determinations in the Venus atmosphere by means of high-resolution spectra from 1 to 2.5 μm

Twenty-one bands of CO₂ and the 2-0 band of CO were analyzed for best temperature and pressure fits from Venus spectra obtained with the “Connes” interferometer at the Steward Observatory 2.25-m telescope during the spring of 1971. An average temperature of 241 ± 7°K, an effective pressure of 0.12 ± 0.06 atm, and an average two-way transmission abundance of 3 km-amagat were determined. No difference in temperature or pressure between hot bands, a double hot band, and regular bands was found. Our results were compared to model calculations for a reflecting layer and scattering atmosphere. The results indicate that, most likely, spectroscopic line formation occurs in a relatively clear space above a scattering cloud layer with a reasonably well-defined upper boundary.     

Mesospheric vertical thermal structure and winds on Venus from HHSMT CO spectral-line observations

We report vertical thermal structure and wind velocities in the Venusian mesosphere retrieved from carbon monoxide (¹²CO J=2-1 and ¹³CO J=2-1) spectral line observations obtained with the Heinrich Hertz Submillimeter Telescope (HHSMT). We observed the mesosphere of Venus from two days after the second Messenger flyby of Venus (on 5 June 2007 at 23:10 UTC) during five days. Day-to-day and day-to-night temperature variations and short-term fluctuations of the mesospheric zonal flow were evident in our data. The extensive layer of warm air detected recently by SPICAV at 90-100 km altitude is also detected in the temperature profiles reported here.These data were part of a coordinated ground-based Venus observational campaign in support of the ESA Venus Express mission. Furthermore, this study attempts to cross-calibrate space- and ground-based observations, to constrain radiative transfer and retrieval algorithms for planetary atmospheres, and to contribute to a more thorough understanding of the global patterns of circulation of the Venusian atmosphere.     

No compelling evidence of distributed production of CO in Comet C/1995 O1 (Hale-Bopp) from millimeter interferometric data and a re-analysis of near-IR lines

Based on long-slit infrared spectroscopic observations, it has been suggested that half of the carbon monoxide present in the atmosphere of Comet C/1995 O1 (Hale-Bopp) close to perihelion was released by a distributed source in the coma, whose nature (dust or gas) remains unidentified. We re-assess the origin of CO in Hale-Bopp’s coma from millimeter interferometric data and a re-analysis of the IR lines.Simultaneous observations of the CO J(1–0) (115 GHz) and J(2–1) (230 GHz) lines were undertaken with the IRAM Plateau de Bure interferometer in single-dish and interferometric modes. The diversity of angular resolutions (from 1700 to 42,000 km diameter at the comet) is suitable to study the radial distribution of CO and detect the extended source observed in the infrared. We used excitation and radiative transfer models to simulate the single-dish and interferometric data. Various CO density distributions were considered, including 3D time-dependent hydrodynamical simulations which reproduce temporal variations caused by the presence of a CO rotating jet. The CO J(1–0) and J(2–1) observations can be consistently explained by a nuclear production of CO. Composite 50:50 nuclear/extended productions with characteristic scale lengths of CO parent L_p > 1500 km are rejected.Based on similar radiation transfer calculations, we show that the CO v = 1–0 ro-vibrational lines observed in Comet Hale-Bopp at heliocentric distances less than 1.5 AU are severely optically thick. The broad extent of the CO brightness distribution in the infrared is mainly due to optical depth effects entering in the emitted radiation. Additional factors can be found in the complex structure of the CO coma, and non-ideal slit positioning caused by the anisotropy of dust IR emission.We conclude that both CO millimeter and infrared lines do not provide compelling evidence for a distributed source of CO in Hale-Bopp’s atmosphere.     

Carbon monoxide frosts in the interstellar medium

Summary The presence of solid carbon monoxide (CO) on interstellar grains was confirmed observationally in 1984 with the detection of infrared absorption at 4.67m wavelength in several molecular clouds. Subsequent observations suggest that solid CO is ubiquitous in the quiescent molecular cloud environment. In some lines of sight, the degree of frosting on to grains is sufficient to reduce appreciably the abundance of CO remaining in the gas, a result of considerable astrophysical significance: in addition to its importance as a tracer of molecular material, CO is vital to the production of many polyatomic molecules by gas phase reaction schemes, and its depletion could have a dramatic effect on the abundances of more complex carbon-bearing molecules. The infrared spectrum of solid CO provides an important diagnostic of the chemical composition and thermal evolution of grain mantles, leading to the prediction that CO₂ is also present in solid form.As it is now some six years since observations of interstellar solid CO were first reported, this is an appropriate time to review the topic and to suggest some directions for future research. The introduction (Sect. 1) attempts to place the subject in its broader astrophysical context. The infrared observations and their implications are discussed in detail in Sect. 2. The question of the degree of CO depletion implied by the observations of both solid state and gas phase CO is re-examined in Sect. 3. We assess the possibility of CO detection by means of solid state absorption or luminescence in the ultraviolet in Sect. 4. Future prospects are summarised in the final section.This article was processed by the author using the Springer-Verlag TEX Theaar macro package 1988.     

Hemispherical distribution of CO above the Venus’ clouds by ground-based 2.3 μm spectroscopy

The abundance of carbon monoxide in the Venus’ dayside atmosphere above the clouds was measured by ground-based 2.3 μm spectroscopy for 4 days. The hemispherical distributions found show no significant latitudinal or longitudinal structure. The disc-averaged mixing ratio of 58 ± 17 ppm found at a representative height of 62-67 km is consistent with previous measurements. Such a flat distribution of CO abundance above the clouds seems to be controlled by an efficient horizontal eddy diffusion with a time scale of 30 days or shorter although the CO distribution below the clouds seems to be controlled by the meridional circulation. The pole-ward wind speed of the meridional circulation above the clouds is estimated to be 0.2 m s⁻¹ or less based on the difference between the CO mixing ratios above and below the clouds.     

Titan’s 5-μm window: observations with the Very Large Telescope

We report on mid-resolution (R∼2000) spectroscopic observations of Titan, acquired in November 2000 with the Very Large Telescope and covering the range 4.75-5.07 μm. These observations provide a detailed characterization of the CO (1-0) vibrational band, clearly separating for the first time individual CO lines (P10 to P19 lines of ¹³CO). They indicate that the CO/N₂ mixing ratio in Titan’s troposphere is 32±10 ppm. Comparison with photochemical models indicates that CO is not in a steady state in Titan’s atmosphere. The observations confirm that Titan’s 5-μm continuum geometric albedo is ∼0.06, and further indicates a ∼20% albedo decrease over 4.98-5.07 μm. Nonzero flux is detected at the 0.01 geometric albedo level in the saturated core of the ¹²CO (1-0) band, at 4.75-4.85 μm, providing evidence for backscattering on the stratospheric haze. Finally, emission lines are detected at 4.75-4.835 μm, coinciding in position with lines from the CO(1-0) and/or CO(2-1) bands. Matching them by thermal emission would require Titan’s stratosphere to be much warmer (by ∼ 25 K at 0.1 mbar) than indicated by the methane 7.7-μm emission and the Voyager radio-occultation. We show instead that a nonthermal mechanism, namely solar-excited fluorescence, is a more plausible source for these emissions. Improved observations and laboratory measurements on the vibrational-translational relaxation of CO are needed for further interpretation of these emissions in terms of a CO stratospheric mixing ratio.     

Laboratory studies of the interaction of carbon monoxide with water ice

The interaction of carbon monoxide (CO) with vapour-deposited water(H₂O) ices has been studied using temperature programmed desorption (TPD) and Fourier transform reflection-absorption infrared spectroscopy (FT-RAIRS) over a range of astrophysically relevant temperatures. Such measurements have shown that CO desorption from amorphous H₂Oices is a much more complex process than current astrochemical models suggest. Re-visiting previously reported laboratory experiments (Collings et al., 2003), a rate model has been constructed to explain, in a phenomenological manner, the desorption of CO over astronomically relevant time scales. The model presented here can be widely applied to a range of astronomical environments where depletion of CO from the gas phase is relevant. The model accounts for the two competing processes of CO desorption and migration, and also enables the entrapment of some of the CO in the ice matrix and its subsequent release as the water ice crystallises and then desorbs. The astronomical implications of this model are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Molecular emission in dense massive clumps from the star-forming regions S231–S235

The paper is concerned with the study of the star-forming regions S231–S235 in radio lines of molecules of the interstellar medium—carbon monoxide (CO), ammonia (NH₃), cyanoacetylene (HC₃N), in maser lines—methanol (CH₃OH) and water vapor (H₂O). The regions S231–S235 belong to the giant molecular cloudG174+2.5. The goal of this paper is to search for new sources of emission toward molecular clumps and to estimate their physical parameters from CO and NH₃ molecular lines. We obtained new detections ofNH₃ andHC₃Nlines in the sources WB89673 and WB89 668 which indicates the presence of high-density gas. From the CO line, we derived sizes, column densities, and masses of molecular clumps. From the NH₃ line, we derived gas kinetic temperatures and number densities in molecular clumps. We determined that kinetic temperatures and number densities of molecular gas are within the limits 16–30 K and 2.8–7.2 × 10³ cm^?3 respectively. The shock-tracing line of CH₃OH molecule at a frequency of 36.2 GHz was detected in WB89 673 for the first time.     

Infrared spectral variations of three Mira variable carbon stars with the 11.3 μm SiC feature

The spectral variations of three Mira variable carbon stars, V CrB, T Dra and V Cyg in the infrared are investigated based on ISO SWS data. It is found that either continua or molecular/dust features were variable with time in the infrared for these carbon stars during one and a half year observations. When stars were brighter the infrared continuum spectra became blue while stars were fainter the infrared continuum spectra became red. In addition, during spectral variations there were the correlation between the 3.05 μm HCN+C₂H₂ and the 5.2 μm C₃ molecular band strengths and the anti-correlation between the 3.05 μm HCN+C₂H₂ molecular band strengths and 13.7 μm C₂H₂ band strengths while during variations the 11.3 μm SiC dust emission strengths were not clearly changed.     

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the CN frequency at 2210 cm⁻¹ in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV spectra of the solid products formed when HCN or CO added to the BGM is similar to the UV absorption formed from the BGM alone. This result is consistent with absence of additional UV chromophores to the solid product when these mixtures are photolyzed. The following photoproducts, which were not starting materials in our photochemical studies, have been observed on Titan: acetonitrile, benzene, diacetylene, ethane, propene, propane, and propyne.     

Electron-impact excitation of the Cameron system (a3π → X1Σ)of CO

We have studied the excitation of the Cameron bands of carbon monoxide (a³π → X¹Σ⁺) by electron impact on CO and CO₂. This investigation was prompted by a recent study of the Martian airglow by Conway (1981) who concluded that the cross section for the dissociative excitation of the Cameron bands is seven times larger than the laboratory value reported by Ajello (1971a) and by a perplexing inconsistency between the optical cross section and CO(a³π) time-of-flight experiments. We have found now that three factors have contributed to these discrepancies: (1) spectral contamination of the (1,4) Cameron band used by Ajello to normalize the entire Cameron band cross section, (2) major revisions in the magnitude of the CO(a³π) radiative lifetime, and (3) new insights into the effects of the CO(a³π) velocity distribution on the field of view of the emission experiments. The new results largely reconcile the TOF and emission measurements, but they also suggest that the calculated photoelectron fluxes in the Martian atmosphere may be too large by a factor of 3.     

The gas composition of jupiter derived from 5-μm airborne spectroscopic observations

The atmospheric transmission window between 1850 and 2250 cm⁻¹ in Jupiter's atmosphere was observed at a spectral resolution of 0.5 cm⁻¹ from the Kuiper Airborne Observatory. The mole fractions of NH₃, PH₃, CH₄, CH₃D, CO, and GeH₄ were derived for the 1- to 6-bar portion of Jupiter's troposphere using a spectrum synthesis program. Knowledge of the abundances of these gases below the visible clouds is necessary to calculate the global inventory of nitrogen, phosphorus, carbon, and deuterium, which, in turn, may constrain models of Jupiter's formation. The N/H ratio is 1.5 ± 0.2 times the value for the Sun's photosphere. The P/H ratio for the 5-bar level is between 1.0 and 1.6 times the solar abundance. The weak ν₃−ν₄ hot band of CH₄ was detected for the first time on Jupiter, thus providing a deep atmospheric value for C/H of 3.6 ± 1.2 times solar. The Jovian deuterium abundance is comparable to that measured in the interstellar medium (D/H = 1.2 ± 0.5) × 10⁻⁵. CO appears to be well mixed with a mole fraction of (1.0 ± 0.3) × 10⁻⁹. Multiple absorption features confirm that GeH₄ is present on Jupiter with a mole fraction of (7.0_−2.0^+4.0) × 10⁻¹⁰. The observed abundances of CO, GeH₄, and PH₃ are consistent with models of convective transport from Jupiter's deep atmosphere.     

Limits on the12C to13C isotopic ratio in two white dwarfs

A search for the molecular¹²C¹³C isotopic bands in two white dwarfs is described. Spectroscopic observations of the two carbon band white dwarfs, BPM 27606 (=2153-51) andL 879-14 (=0435-08) have been obtained. These data have a resolution slightly better than 2 Å, higher than usually employed for white dwarfs and cover the v=1 vibrational swan bands of the C₂ molecule where the isotopic shift is of order 8 Å. The isotopic bands have not been detected. However, upper limits to the¹²C:¹³C abundance ratio derived from the data yield¹²C:¹³C>40 for BPM 27606 and¹²C:¹³C>8 for L879-14. If these ratios are representative of the material in the interiors of the carbon band white dwarfs and taking the low upper limits on the N and O abundances relative to C, this is consistent with the carbon having been formed by the 3 process and not having undergone any subsequent mixing with H-rich material. In addition, the C₂ vibrational bandheads are blueshifted, most probably by pressure shifts. This shows that the employment of higher resolutions reveals additional physical effects in the spectra of the carbon band white dwarfs that may become important for interpreting the cool end of the helium rich white dwarf sequence.