The infrared spectra of nitriles and related compounds frozen in Ar and H2O

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.     

The discovery of a new infrared emission feature at 1905 wavenumbers (5.25 microns) in the spectrum of BD +30 degrees 3639 and its relation to the polycyclic aromatic hydrocarbon model

We have discovered a new IR emission feature at 1905 cm-1 (5.25 microns) in the spectrum of BD +30 degrees 3639. This feature joins the family of well-known IR emission features at 3040, 2940, 1750, 1610, "1310," 1160, and 890 cm-1 (3.3, 3.4, 5.7, 6.2, "7.7," 8.6, and 11.2 microns). The origin of this new feature is discussed and it is assigned to an overtone or combination band involving C-H bending modes of polycyclic aromatic hydrocarbons (PAHs). Laboratory work suggests that spectral studies of the 2000-1650 cm-1 (5.0-6.1 microns) region may be very useful in elucidating the molecular structure of interstellar PAHs. The new feature, in conjunction with other recently discovered spectral structure, suggests that the narrow IR emission features originate in PAH molecules rather than large carbon grains. Larger species are likely to be the source of the broad underlying "plateaus" seen in many of the spectra.     

The physical and infrared spectral properties of CO2 in astrophysical ice analogs

Both laboratory measurements and theory indicate that CO2 should be a common component in interstellar ices. We show that the exact band position, width, and profile of the solid-state 12CO2 infrared bands near 3705, 3600, 2340, and 660 cm-1 (2.70, 2.78, 4.27, and 15.2 micrometers) and the 13CO2 band near 2280 cm-1 (4.39 micrometers) are dependent on the matrix in which the CO2 is frozen. Measurements of these bands in astronomical spectra can be used to determine column densities of solid-state CO2 and provide important information on the physical conditions present in the ice grains of which the CO2 is a part. Depending on the composition of the ice, the CO2 asymmetric stretching band was observed to vary from 2328.7 to 2346.0 cm-1 and have full widths at half-maxima (FWHMs) ranging from 4.7 to 29.9 cm-1. The other CO2 bands showed similar variations. Both position and width are also concentration dependent. Absorption coefficients were determined for the five CO2 bands. These were found to be temperature independent for CO2 in CO and CO2 matrices but varied slightly with temperature for CO2 in H2O-rich ices. For all five bands this variation was found to be less than 15% from 10 to 150 K, the temperature at which H2O ice sublimes. A number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices were also determined. The CO2-CO2 surface binding energy in pure CO2 ices is found to be (delta Hs/k) = 2690 +/- 50 K. CO2-H2O and CO-H2O surface binding energies were determined to be (delta Hs/k) = 2860 +/- 200 K and 1740 +/- 100 K, respectively. Under our experimental conditions, CO2 condenses in measurable quantities into H2O-rich ices at temperatures up to 100 K, only slightly higher than the temperature at which pure CO2 condenses. Once frozen into an H2O-rich ice, the subsequent loss of CO2 upon warming is highly dependent on concentration. For ices with H2O/CO2 > 20, the CO is physically trapped within the H2O lattice, and little CO2 is lost until the sublimation temperature of the H2O matrix is reached. In contrast, in ices having H2O/CO2 < 5, the CO2 remains only to temperatures of about 90 K. Above this point the CO2 readily diffuses out of the H2O matrix. These results suggest that two different forms of H2O lattice are produced. The implications of these data for cometary models and our understanding of cometary formation are considered.     

Hydrogenated polycyclic aromatic hydrocarbons and the 2940 and 2850 wavenumber (3.40 and 3.51 micron) infrared emission features

The 3150-2700 cm-1 (3.17-3.70 microns) range of the spectra of a number of Ar-matrix-isolated PAHs containing excess H atoms (Hn-PAHs) are presented. This region covers features produced by aromatic and aliphatic C-H stretching vibrations as well as overtone and combination bands involving lower lying fundamentals. The aliphatic C-H stretches in molecules of this type having low to modest excess H coverage provide excellent fits to a number of the weak emission features superposed on the plateau between 3080 and 2700 cm-1 (3.25 and 3.7 microns) in the spectra of many planetary nebulae, reflection nebulae, and H II regions. Higher H coverage is implied for a few objects. We compare these results in context with the other suggested identifications of the emission features in the 2950-2700 cm-1 (3.39-3.70 microns) region and briefly discuss their astrophysical implications.     

New emission features in the 11-13 micron region and their relationship to polycyclic aromatic hydrocarbons

If the "11.3 microns" emission feature seen in the spectra of many planetary nebulae, H II regions, and reflection nebulae is due to polycyclic aromatic hydrocarbons (PAHs), then additional features should be present between 11.3 and 13.0 microns (885 and 770 cm-1). Moderate-resolution spectra of NGC 7027, HD 44179, IRAS 21282+5050, and BD + 30 degrees 3639 are presented which show that the "11.3 microns" feature actually peaks at 11.22 microns (891 cm-1). The spectra also show evidence of new emission features near 11.9 and 12.7 microns (840 and 787 cm-1). These are consistent with an origin from PAHs and can be used to constrain the molecular structure of the family of PAHs responsible for the infrared features. The observed asymmetry of the "11.3 microns" band is consistent with the slight anharmonicity expected in the C--H out-of-plane bending mode in PAHs. Laboratory experiments show that the intensity of this mode relative to the higher frequency modes depends on the extent of molecular "clustering." The observed strengths of the "11.3 microns" interstellar bands relative to the higher frequency bands are most consistent with the features originating from free molecular PAHs. The intensity and profile of the underlying broad structure, however, may well arise from PAH clusters and amorphous carbon particles. Analysis of the 11-13 microns (910-770 cm-1) emission suggests that the molecular structures of the most intensity emitting free PAHs vary somewhat between the high-excitation environment in NGC 7027 and the low-excitation but high-flux environment close to HD 44179. Finally, a previously undetected series of regularly spaced features between 10 and 11 microns (1000 and 910 cm-1) in the spectrum of HD 44179 suggests that a simple polyatomic hydride is present in the gas phase in this object.     

Insoluble organic material of the Orgueil carbonaceous chondrite and the unidentified infrared bands

Deuterium abundance measurements and the 13C NMR spectrum of the HF/HCl insoluble residue of the Orgueil carbonaceous chondrite indicate the presence of an extensive component of polycyclic aromatic hydrocarbons (PAH) that is of possible interstellar origin or is similar to PAH hypothesized to exist in interstellar space. Infrared spectra have been obtained using an FTIR spectrometer of the acid insoluble residue, the residue after heating in vacuum, and condensate. Bulk acid insoluble residue was pressed into KBr pellets and also heated under high vacuum to sublimate a volatile component onto KBr disks. The remaining non-volatile organic component of the Orgueil meteorite from such evaporations pressed into KBr pellets exhibits a spectral signature similar to that observed in emission from the Orion Nebula and found in Raman spectra of interplanetary dust particles (IDPs). In addition it has an 11.3 microns (885 cm-1) band indicating PAH having single hydrogens per peripheral aromatic ring. We conclude the nonvolatile material is similar to interstellar PAH because the observed 11.3 microns (885 cm-1) unidentified infrared (UIR) emission suggests interstellar PAH have single hydrogens per peripheral aromatic ring. The volatile fraction of the Orgueil shows an aliphatic CH stretch feature and its spectrum in the 2-25 microns range is similar to that of the bulk residue.     

Infrared spectroscopy of Triton and Pluto ice analogs: the case for saturated hydrocarbons

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton and Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450 cm-1 (2.25 micrometers) and extends to lower frequencies, may be due to alkanes (C(n)H2n+2) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemistry of N2:CH4 and N(2):CH4:CO ices was explored demonstrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances. For example, using these A values the abundance ratios CH4/N2 approximately 1.3 x 10(-3), C2H4/N2 < or = 9.5 x 10(-7) and H2CO/N2 < or = 7.8 x 10(-7) are deduced for Triton and CH4/N2 approximately 3.1 x 10(-3), C2H4/N2 < or = 4.1 x 10(-6), and H2CO/N2 < or = 5.2 x 10(-6) deduced for Pluto. The small amounts of C2H4 and H2CO in the surface ices of these bodies are in disagreement with the large abundances expected from many theoretical models.     

Heterodyne spectroscopy of the 158 micron C II line in M42

We have obtained velocity-resolved spectra of the 12C II 157.8 microns 2P3/2-2P1/2 fine structure line in the M42 region of Orion. Observations at 0.8 km s-1 resolution with a laser heterodyne spectrometer show multiple velocity components in some locations, with typical linewidths of 3-5 km s-1. Spectra of theta 1C and BN-KL also show weak emission from the F = 2-1 hyperfine component of the equivalent 13C II line. From the observed 12C II/13C II line intensity ratios, we deduce that the 12C II emission is optically thick with tau approximately 5 at both positions. Excitation temperatures of 128 K and 90 K, together with column densities of approximately 1 x 10(19) cm-2 and approximately 4 x 10(18) cm-2, are derived for theta 1C and BN-KL, respectively.     

Absorption Features of Ices Toward NGC7538 IRS1

In this paper we present a comparison of the observed absorption band at about 660 cm-1 (15.1 μm) toward NGC7538 IRS1 attributed to the bending mode of solid CO2 with laboratory spectra of ion irradiated mixtures. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

An upper limit to the acetylene abundance toward BN in the Orion molecular cloud

We report a search for the acetylene (C2H2) nu 3 infrared vibration-rotation absorption near 3 micrometers toward the Becklin-Neugebauer source in the Orion molecular cloud. The relative abundance of C2H2/CO in the quiescent gas (9 km s-1 component) is less than 3 x 10(-3) (5 sigma).     

Heterodyne spectroscopy of the J = 17-16 CO line in Orion

We have obtained high-resolution spectra of the 153 micrometers J = 17-16 CO line in the BN-KL region of Orion using a laser heterodyne spectrometer. The line shows broad wings (30 km s-1 FWHM at BN) characteristic of the plateau emission as well as a narrower component probably associated with the quiescent gas in the molecular ridge. From an analysis of the plateau emission together with that observed in lower J CO transitions, we derive an excitation temperature of 180 +/- 50 K and minimum column density of 1 x 10(18) cm-2 for CO in this component, which constitutes 80% of the total integrated intensity of the J = 17-16 line near BN. The peak intensity of the narrower component observed at 0.8 km s-1 resolution increases relative to that of the plateau component toward theta 1C and away from BN, while the width decreases from 10 to 4 km s-1 (FWHM).     

Probing the surfaces of interstellar dust grains: the adsorption of CO at bare grain surfaces

A solid-state feature was detected at around 2175 cm⁻¹ towards 30 embedded young stellar objects in spectra obtained using the Infrared Spectrometer and Array Camera at the European Southern Observatory Very Large Telescope. We present results from laboratory studies of CO adsorbed at the surface of zeolite wafers, where absorption bands were detected at 2177 and 2168 cm⁻¹ (corresponding to CO chemisorbed at the zeolite surface) and 2130 cm⁻¹ (corresponding to CO physisorbed at the zeolite surface), providing an excellent match to the observational data. We propose that the main carrier of the 2175-band is CO chemisorbed at bare surfaces of dust grains in the interstellar medium. This result provides the first direct evidence that gas–surface interactions do not have to result in the formation of ice mantles on interstellar dust. The strength of the 2175-band is estimated to be  ∼4 × 10⁻¹⁹ cm  molecule⁻¹. The abundance of CO adsorbed at bare grain surfaces ranges from 0.06 to 0.16 relative to H₂O ice, which is, at most, half of the abundance (relative to H₂O ice) of CO residing in H₂O-dominated ice environments. These findings imply that interstellar grains have a large (catalytically active) surface area, providing a refuge for interstellar species. Consequently, the potential exists for heterogeneous chemistry to occur involving CO molecules in unique surface chemistry pathways not currently considered in gas grain models of the interstellar medium.     

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.     

1300 micron continuum and C18O line mapping of giant molecular cloud cores. II. W3, NGC 2264, NGC 6334I, RHO Ophiuchi and S140

In this paper we present nearly simultaneous 1300 microns continuum and J = 2-1 C18O maps of the cores of five molecular clouds, W3, NGC 2264, NGC 6334I, rho Oph, and S140. The purpose of this experiment was to compare these two column density tracers. We find that dust continuum and C18O emission are equally effective tracers of column density in molecular cloud cores and give a good indication of cloud structure. When the maps are analyzed in terms of the quantity q = Q/[a rho RX(C18O)], we find that q does not vary by much more than an order of magnitude either within objects or from object to object, implying that nominal dust parameters of absorption efficiency, radius, and gas-to-dust ratio and CO abundance are on average correct in a variety of sources. We did detect source-to-source variations in q. This variation could be either in the dust-to-CO number density ratio or in grain parameters. These variations are not well correlated with total source luminosity, average or typical temperature, or total column density. The best example of this variation appears to be rho Oph where q is about a factor of 7 lower than is typically found. Our approach is analogous to the study of the A nu to CO ratio and is probably equivalent to extending this study to large A nu if the same grains are responsible for both optical opacity and far-infrared to millimeter-wave emission. There is no fundamental reason to expect A nu/NCO or q to be constant and, in fact, we have found that it is not constant in even a small source sample.     

Observations of interstellar HOCO+: abundance enhancements toward the galactic center

A survey of the 4(04)-3(03) and 1(01)-0(00) transitions of HOCO+ has been made toward several molecular clouds. The HOCO+ molecule was not observed in any sources except Sgr B2 and Sgr A. The 5(05)-4(04) and 4(14)-3(13) transitions were also detected toward Sgr B2. The results indicate that gas phase CO2 is not a major carbon reservoir in typical molecular clouds. In Sgr B2, the HOCO+ antenna temperature exhibits a peak approximately 2' north of the Sgr B2 central position (Sgr B2[M]) and the 4(04)-3(03) line emission is extended over a approximately 10' x 10' region. The column density of HOCO+ at the northern peak in Sgr B2 is approximately 3 x 10(14) cm-2, and the fractional abundance relative to H2 > or = 3 x 10(-10), which is about 2 orders of magnitude greater than recent predictions of quiescent cloud ion-molecule chemistry.     

Shock chemistry in the molecular clouds associated with SNR IC 443

Several interstellar molecules have been detected toward the highly perturbed B and G clouds associated with the supernova remnant IC 443 via their 3 mm transitions, including N2H+, SiO, SO, CN, HNC, and H13CO+. The (J, K) = (1, 1) and (2, 2) inversion lines of metastable ammonia have also been observed, as well as the J = 3-2 transition of HCO+ at 1.2 mm. Analysis of the (1, 1) and (2, 2) inversion lines of NH3 indicates minimum gas kinetic temperatures of TK = 70 K toward cloud B, and TK = 33 K in cloud G. Modeling of the J = 1-0 and J = 3-2 transitions of HCO+ implies densities greater than 10(5) cm-3 toward both positions. These data clearly show that hot and dense material is present in IC 443, and they suggest the presence of shocks in both regions. A careful analysis of the HCO+ lines indicates that the HCO+ abundance is at most enhanced by factors of a few over that found in cold, quiescent gas. This conclusion contradicts past claims of HCO+ abundance enhancements of several orders of magnitude in the perturbed regions. The N2H+ abundance was also found to be similar to that in cold gas, suggesting that there is no increase in ionization in the clouds. The abundances of SO and CS, as well as CN and NH3, do not appear to differ significantly from those found in cold dark clouds, although chemistry models predict sulfur-containing species to undergo high-temperature enhancements. SiO, however, is found to have an abundance in the perturbed gas 100 times larger than the upper limits observed in the dark cloud TMC 1, a result in agreement with high temperature chemistry models. In addition, the HNC/HCN ratio in both IC 443 B and G was found to be approximately 0.1--far from the ratio of 1 predicted by low-temperature ion-molecule chemistry, but similar to the values observed in clouds where elevated temperatures are present.     

A photochemical model of the martian atmosphere

The factors governing the amounts of CO, O2, and O3 in the martian atmosphere are investigated using a minimally constrained, one-dimensional photochemical model. We find that the incorporation of temperature-dependent CO2 absorption cross sections leads to an enhancement in the water photolysis rate, increasing the abundance of OH radicals to the point where the model CO abundance is smaller than observed. Good agreement between models and observations of CO, O2, O3, and the escape flux of atomic hydrogen can be achieved, using only gas-phase chemistry, by varying the recommended rate constants for the reactions CO + OH and OH + HO2 within their specified uncertainties. Similar revisions have been suggested to resolve discrepancies between models and observations of the terrestrial mesosphere. The oxygen escape flux plays a key role in the oxygen budget on Mars; as inferred from the observed atomic hydrogen escape, it is much larger than recent calculations of the exospheric escape rate for oxygen. Weathering of the surface may account for the imbalance. Quantification of the escape rates of oxygen and hydrogen from Mars is a worthwhile objective for an upcoming martian upper atmospheric mission. We also consider the possibility that HOx radicals may be catalytically destroyed on dust grains suspended in the atmosphere. Good agreement with the observed CO mixing ratio can be achieved via this mechanism, but the resulting ozone column is much higher than the observed quantity. We feel that there is no need at this time to invoke heterogeneous processes to reconcile models and observations.     

H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, phi H2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi H2SO4 = 2.2 x 10(12) cm-2 sec-1. The sulfur to sulfuric acid mass flux ratio in the clouds is 1 : 27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3 km-1 in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(12) cm-2 sec-1 in this model. Our second model, which is constrained to yield fH2SO4 = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O(30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; phi H2SO4 = 6.4 x 10(12) cm-2 sec-1; and phi co = 4.2 x 10(12) cm-2 sec-1. The S/H2SO4 flux mass ratio is 1 : 18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km-1 in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of formation of the lower cloud layer. Variations of the lower cloud layer are discussed. Our modeling of the OCS and CO profiles in the lower atmosphere measured by Pollack et al. (1993) provides a reasonable explanation of these data and shows that the rate coefficient of the reaction SO3 + CO --> CO2 + SO2 is equal to 10(-11) exp(-(13,100 +/- 1000)/T) cm3/s. The main channel of the reaction between SO3 and OCS is CO2 + (SO)2, and its rate coefficient is equal to 10(-11) exp(-(8900 +/- 500)T)cm3/s. In the conditions of Venus' lower atmosphere, (SO)2 is removed by the reaction (SO)2 + OCS --> CO + S2 + SO2. The model predicts an OCS mixing ratio of 28 ppm near the surface.     

Clouds, hazes, and the stratospheric methane abundance in Neptune

Analysis of high-spatial-resolution (approximately 0.8 arcsec) methane band and continuum imagery of Neptune's relatively homogeneous Equatorial Region yields significant constraints on (1) the stratospheric gaseous methane mixing ratio (fCH4,s), (2) the column abundances and optical properties of stratospheric and tropospheric hydrocarbon hazes, and (3) the wavelength-dependent single-scattering albedo of the 3-bar opaque cloud. From the center-to-limb behavior of the 7270-angstroms and 8900-angstrom sCH4 bands, the stratospheric methane mixing ratio is limited to fCH4,s < 1.7 x 10(-3), with a nominal value of fCH4,s = 3.5 x 10(-4), one to two orders of magnitude less than pre-Voyager estimates, but in agreement with a number of recent ultraviolet and thermal infrared measurements, and largely in agreement with the tropopause mixing ratio implied by Voyager temperature measurements. Upper limits to the stratospheric haze mass column abundance and 6190-angstroms and 8900-angstroms haze opacities are 0.61 microgram cm-2 and 0.075 and 0.042, respectively, with nominal values of 0.20 microgram cm-2 and 0.025 and 0.014 for the 0.2-micrometer radius particles preferred by the recent Voyager PPS analysis of Pryor et al. (1992, Icarus 99, 302-316). The tropospheric CH4 haze opacities are comparable to that found in the stratosphere, upper limits of 0.104 and 0.065 at 6190 angstroms and 8900 angstroms, respectively, with nominal values of 0.085 and 0.058. This indicates a column abundance less than 11.0 micrograms cm-2, corresponding to the methane gas content within a well-mixed 3% methane tropospheric layer only 0.1 cm thick near the 1.5-bar CH4 condensation level. Constraints on the single-scattering albedos of these hazes include (1) for the stratospheric component, 6190-angstroms and 8900-angstroms imaginary indices of refraction less than 0.047 and 0.099, respectively, with 0.000 (conservative scattering) being the nominal value at both wavelengths, and (2) CH4 haze single-scattering albedos greater than 0.85 and 0.50 at these two wavelengths, with conservative scattering again begin the preferred value. However, conservative scattering is ruled out for the opaque cloud near 3 bars marking the bottom of the visible atmosphere. Specifically, we find cloud single-scattering albedos of 0.915 +/- 0.006 at 6340 angstroms, 0.775 +/- 0.012 at 7490 angstroms, and 0.803 +/- 0.010 at 8260 angstrom. Global models utilizing a complete global spectrum confirm the red-absorbing character of the 3-bar cloud. The global-mean model has approximately 7.7 times greater stratospheric aerosol content then the Equatorial Region. An analysis of stratospheric haze precipitation rates indicates a steady-state haze production rate of 0.185-1.5 x 10(-14) g cm-2 sec-1, in agreement with recent theoretical photochemical estimates. Finally, reanalysis of the Voyager PPS 7500-angstroms phase angle data utilizing the fCH4,s value derived here confirms the Pryor et al. result of a tropospheric CH4 haze opacity of a few tenths in the 22-30 degrees S latitude region, several times that of the Equatorial Region or of the globe. The factor-of-10 reduction in fCH4,s below that assumed by Pryor et al. implies decreased gas absorption and consequently a decrease in the forward-scattering component of tropospheric aerosols.