Chemical kinetic model for the lower atmosphere of Venus

A self-consistent chemical kinetic model of the Venus atmosphere at 0-47 km has been calculated for the first time. The model involves 82 reactions of 26 species. Chemical processes in the atmosphere below the clouds are initiated by photochemical products from the middle atmosphere (H₂SO₄, CO, S_x), thermochemistry in the lowest 10 km, and photolysis of S₃. The sulfur bonds in OCS and S_x are weaker than the bonds of other elements in the basic atmospheric species on Venus; therefore the chemistry is mostly sulfur-driven. Sulfur chemistry activates some H and Cl atoms and radicals, though their effect on the chemical composition is weak. The lack of kinetic data for many reactions presents a problem that has been solved using some similar reactions and thermodynamic calculations of inverse processes. Column rates of some reactions in the lower atmosphere exceed the highest rates in the middle atmosphere by two orders of magnitude. However, many reactions are balanced by the inverse processes, and their net rates are comparable to those in the middle atmosphere. The calculated profile of CO is in excellent agreement with the Pioneer Venus and Venera 12 gas chromatographic measurements and slightly above the values from the nightside spectroscopy at 2.3 μm. The OCS profile also agrees with the nightside spectroscopy which is the only source of data for this species. The abundance and vertical profile of gaseous H₂SO₄ are similar to those observed by the Mariner 10 and Magellan radio occultations and ground-based microwave telescopes. While the calculated mean S₃ abundance agrees with the Venera 11-14 observations, a steep decrease in S₃ from the surface to 20 km is not expected from the observations. The ClSO₂ and SO₂Cl₂ mixing ratios are ∼10⁻¹¹ in the lowest scale height. The existing concept of the atmospheric sulfur cycles is incompatible with the observations of the OCS profile. A scheme suggested in the current work involves the basic photochemical cycle, that transforms CO₂ and SO₂ into SO₃, CO, and S_x, and a minor photochemical cycle which forms CO and S_x from OCS. The net effect of thermochemistry in the lowest 10 km is formation of OCS from CO and S_x. Chemistry at 30-40 km removes the downward flux of SO₃ and the upward flux of OCS and increases the downward fluxes of CO and S_x. The geological cycle of sulfur remains unchanged.     

Are the clouds of venus sulfuric acid?

Water solutions of sulfuric acid, containing about 75% H₂SO₄ by weight, have a refractive index within 0.01 of the values deduced from polarimetric observations of the Venus clouds. These solutions remain liquid at the cloud temperature, thus explaining the spherical shape of the cloud particles (droplets). The equilibrium vapor pressure of water above such solutions is 0.01 that of liquid water or ice, which accounts for the observed dryness of the cloud region. Furthermore, H₂SO₄ solutions of such concentration have spectra very similar to Venus in the 8–13 μm region; in particular, they explain the 11.2 μm band. Cold sulfuric acid solutions also seem consistent with Venus spectra in the 3–4 μm region. The amount of acid required to make the visible clouds is quite small, and is consistent with both the cosmic abundance of sulfur and the degree of out-gassing of the planet indicated by known atmospheric constituents. Sulfuric acid occurs naturally in volcanic gases, along with known constituents of the Venus atmosphere such as CO₂, HCl, and HF ; it is produced at high temperature by reactions between these gases and common sulfate rocks. The great stability and low vapor pressure of H₂SO₄ and its water solutions explain the lack of other sulfur compounds in the atmosphere of Venus—a lack that is otherwise puzzling.Sulfuric acid precipitation may explain some peculiarities in Venera and Mariner data. Because sulfuric acid solutions are in good agreement with the Venus data, and because no other material that has been proposed is even consistent with the polarimetric and spectroscopic data, H₂SO₄ must be considered the most probable constituent of the Venus clouds.     

Microwave Remote Sensing of the Temperature and Distribution of Sulfur Compounds in the Lower Atmosphere of Venus

A multi-wavelength radio frequency observation of Venus was performed on April 5, 1996, with the Very Large Array to investigate potential variations in the vertical and horizontal distribution of temperature and the sulfur compounds sulfur dioxide (SO₂) and sulfuric acid vapor (H₂SO₄(g)) in the atmosphere of the planet. Brightness temperature maps were produced which feature significantly darkened polar regions compared to the brighter low-latitude regions at both observed frequencies. This is the first time such polar features have been seen unambiguously in radio wavelength observations of Venus. The limb-darkening displayed in the maps helps to constrain the vertical profile of H₂SO₄(g), temperature, and to some degree SO₂. The maps were interpreted by applying a retrieval algorithm to produce vertical profiles of temperature and abundance of H₂SO₄(g) given an assumed sub-cloud abundance of SO₂. The results indicate a substantially higher abundance of H₂SO₄(g) at high latitudes (above 45°) than in the low-latitude regions. The retrieved temperature profiles are up to 25 K warmer than the profile obtained by the Pioneer Venus sounder probe at altitudes below 40 km (depending on location and assumed SO₂ abundance). For 150 ppm of SO₂, it is more consistent with the temperature profile obtained by Mariner 5, extrapolated to the surface via a dry adiabat. The profiles obtained for H₂SO₄(g) at high latitudes are consistent with those derived from the Magellan radio occultation experiments, peaking at around 8 ppm at an altitude of 46 km and decaying rapidly away from that altitude. At low latitudes, no significant H₂SO₄(g) is observed, regardless of the assumed SO₂ content. This is well below that measured by Mariner 10 (Lipa and Tyler 1979, Icarus39, 192-208), which peaked at ∼14 ppm near 47 km. Our results favor ≤100 ppm of SO₂ at low latitudes and ≤50 ppm in polar regions. The low-latitude value is statistically consistent with the results of Bézard et al. (1983, Geophs. Res. Lett.20, 1587-1590), who found that a sub-cloud SO₂ abundance of 130±40 ppm best matched their observations in the near-IR. The retrieved temperature profile and higher abundance of H₂SO₄(g) in polar regions are consistent with a strong equatorial-to-polar, cloud-level flow due to a Hadley cell in the atmosphere of Venus.     

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.     

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.     

Sulfuric acid aerosols in the atmospheres of the terrestrial planets

Clouds and hazes composed of sulfuric acid are observed to exist or postulated to have once existed on each of the terrestrial planets with atmospheres in our solar system. Venus today maintains a global cover of clouds composed of a sulfuric acid/water solution that extends in altitude from roughly 50 km to roughly 80 km. Terrestrial polar stratospheric clouds (PSCs) form on stratospheric sulfuric acid aerosols, and both PSCs and stratospheric aerosols play a critical role in the formation of the ozone hole. Stratospheric aerosols can modify the climate when they are enhanced following volcanic eruptions, and are a current focus for geoengineering studies. Rain is made more acidic by sulfuric acid originating from sulfur dioxide generated by industry on Earth. Analysis of the sulfur content of Martian rocks has led to the hypothesis that an early Martian atmosphere, rich in SO₂ and H₂O, could support a sulfur-infused hydrological cycle. Here we consider the plausibility of frozen sulfuric acid in the upper clouds of Venus, which could lead to lightning generation, with implications for observations by the European Space Agency's Venus Express and the Japan Aerospace Exploration Agency's Venus Climate Orbiter (also known as Akatsuki). We also present simulations of a sulfur-rich early Martian atmosphere. We find that about 40 cm/yr of precipitation having a pH of about 2.0 could fall in an early Martian atmosphere, assuming a surface temperature of 273 K, and SO₂ generation rates consistent with the formation of Tharsis. This modeled acid rain is a powerful sink for SO₂, quickly removing it and preventing it from having a significant greenhouse effect.     

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.     

Photochemistry of the stratosphere of Venus: Implications for atmospheric evolution

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, combined with the results of recent observations and laboratory studies. We examined three models, with H₂ mixing ratio equal to 2 × 10^?5, 5 × 10^?7, and 1 × 10^?13, respectively. All models satisfactorily account for the observations of CO, O₂, O₂(¹Δ), and SO₂ in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the uv albedo. Oxygen, derived from CO₂ photolysis, is primarily consumed by CO₂ recombination and oxidation of SO₂ to H₂SO₄. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO₂ by O occurs in the lower stratosphere. In the high-H₂ model (model A) the OO bond is broken mainly by S + O₂ and SO + HO₂. In the low-H₂ models additional reactions for breaking the OO bond must be invoked: NO + HO₂ in model B and ClCO + O₂ in model C. It is shown that lightning in the lower atmosphere could provide as much as 30 ppb of NO_x in the stratosphere. Our modeling reveals a number of intriguing similarities, previously unsuspected, between the chemistry of the stratosphere of Venus and that of the Earth. Photochemistry may have played a major role in the evolution of the atmosphere. The current atmosphere, as described by our preferred model, is characterized by an extreme deficiency of hydrogen species, having probably lost the equivalent of 10²–10³ times the present hydrogen content.     

Vertical profiling of SO2 and SO above Venus’ clouds by SPICAV/SOIR solar occultations

New measurements of sulfur dioxide (SO₂) and monoxide (SO) in the atmosphere of Venus by SPICAV/SOIR instrument onboard Venus Express orbiter provide ample statistics to study the behavior of these gases above Venus’ clouds. The instrument (a set of three spectrometers) is capable to sound atmospheric structure above the clouds in several observation modes (nadir, solar and stellar occultations) either in the UV or in the near IR spectral ranges. We present the results from solar occultations in the absorption ranges of SO₂ (190–230 nm, and at 4 μm) and SO (190–230 nm). The dioxide was detected by the SOIR spectrometer at the altitudes of 65–80 km in the IR and by the SPICAV spectrometer at 85–105 km in the UV. The monoxide’s absorption was measured only by SPICAV at 85–105 km. We analyzed 39 sessions of solar occultation, where boresights of both spectrometers are oriented identically, to provide complete vertical profiling of SO₂ of the Venus’ mesosphere (65–105 km). Here we report the first firm detection and measurements of two SO₂ layers. In the lower layer SO₂ mixing ratio is within 0.02–0.5 ppmv. The upper layer, also conceivable from microwave measurements by Sandor et al. (Sandor, B.J., Todd Clancy, R., Moriarty-Schieven, G., Mills, F.P. [2010]. Icarus 208, 49–60) is characterized by SO₂ increasing with the altitude from 0.05 to 2 ppmv, and the [SO₂]/[SO] ratio varying from 1 to 5. The presence of the high-altitude SO_x species could be explained by H₂SO₄ photodissociation under somewhat warmer temperature conditions in Venus mesosphere. At 90–100 km the content of the sulfur dioxide correlates with temperature increasing from 0.1 ppmv at 165–170 K to 0.5–1 ppmv at 190–192 K. It supports the hypothesis of SO₂ production by the evaporation of H₂SO₄ from droplets and its subsequent photolysis at around 100 km.     

Laboratory studies on the reactions between Chlorine,Sulfur Dioxide,and Oxygen: Implications for the Venus Stratosphere

The title reaction was studied by photolyzing mixtures of Cl₂ and SO₂ with and without O₂ present in an atmosphere of N₂, using Fourier transform infrared spectrophotometry to monitor reactants and products. In the absence of oxygen, sulfur dioxide is quantitatively converted to sulfuryl chloride. With 10 to 150 Torr O₂ present H₂SO₄ is produced as well as SO₂Cl₂. When a number of speculative reactions inferred from these experiments are added to a published model for Venus stratospheric chemistry, it emerges that SO₂Cl₂ is a key reservoir species for chlorine and that the reaction between Cl and So₂ provides an important cycle for destroying O₂ and converting SO₂ to H₂So₄. The modified model could provide a possible solution to the photochemistry of the Venus stratosphere if the mixing ratio of chlorine on Venus were as high as 8 ppm.     

Upper limits for H2SO4 in the mesosphere of Venus

Rapid temporal variability of SO₂ and SO in the Venus 85–100 km mesosphere (Sandor, B.J., Clancy, R.T., Moriarty-Schieven G.H. [2007]. Bull. Am. Astron. Soc. 39, 503; Sandor, B.J., Clancy, R.T., Moriarty-Schieven, G.H., Mills, F.P. [2010]. Icarus 208, 49–60) requires in situ sources and sinks for these molecules. While many loss mechanisms are recognized, no process for in situ production is known. Observational investigations to find, or constrain other potential sulfur reservoirs offer one method toward understanding the applicable photochemistry. Here, we report upper limits for gas-phase H₂SO₄ (sulfuric acid) abundances in Venus’ 85–100 km upper mesosphere, derived from 16 ground-based sub-mm spectroscopic observations in the period 2004–2008. Unlike the ubiquitous sulfuric acid solid/liquid aerosol, the gas phase would be photochemically active, potentially both source and sink for SO and SO₂. H₂SO₄ is retrieved from sub-mm lines located in the same bandpass as the SO₂ and SO lines described by Sandor et al. (Sandor, B.J., Clancy, R.T., Moriarty-Schieven, G.H., Mills, F.P. [2010]. Icarus 208, 49–60). H₂SO₄ upper limits reported here are thus simultaneous and spatially coincident with measurements of SO₂ and SO, providing for analysis of the three sulfur species collectively. The average H₂SO₄ abundance over 16 observations is 1 ± 2 ppb (i.e. <3 ppb). Upper limits for individual observations range from 3 to 44 ppb, where quality of the observing weather is the dominant constraint on measurement precision. The sum of H₂SO₄, SO₂ and SO varies widely. In one comparison, the sum [H₂SO₄ + SO₂ + SO] measured on one date differs by 10-σ from the sum measured 2 months later. We conclude that upper mesospheric sulfur atoms are not conserved among the three molecules, that H₂SO₄ is not a significant sulfur reservoir for balancing the observed variations of [SO₂ + SO], and is not relevant to the (still unknown) photochemistry responsible for observed behavior of SO₂ and SO. Having ruled out H₂SO₄, we infer that elemental sulfur is the most probable candidate for the needed third reservoir.     

Cloud base levels for Jupiter and Venus and the heteromolecular nucleation theory

For purified binary gas mixtures like NH₃H₂O or HClH₂O, partial pressures appreciably greater than the two saturation partial pressures are needed to condense the gas mixture into small solution droplets (“homogeneous hetero-molecular nucleation”). Thus without foreign nuclei, clouds are not as easily formed as in the theories of Lewis; the latter should be valid only if large condensation nuclei are available. We calculate here from classical homogeneous heteromolecular nucleation theory the threshold partial pressures necessary to achieve droplet nucleation for the gas mixtures NH₃H₂O (Jupiter,…), HClH₂O (Venus), H₂SO₄H₂O (Venus), and C₂H₅OHH₂O (laboratory). In the last case, theory and experiment agree satisfactorily. If no “dust” particles are available as condensation nuclei, then we expect in Jupiter's atmosphere the cloud base level to be around 40 km above the 400K level instead of 10–25 km in Lewis' models (1969) (similar upward shifts for the outer Jovian planets). For Venus, our corrections make the formation of HClH₂O clouds less probable for the 60-km layer at 0°C. If H₂SO₄ is formed by (photo-)chemical oxidation of SO₂ and if clouds are formed at that level where the H₂SO₄ production is largest, then the cloud base levels for H₂SO₄H₂O mixture clouds will not be shifted by our nucleation effects. For more reliable predictions, one needs more accurate data on the water vapor content of the planetary atmospheres and laboratory experiments testing the theoretically predicted nucleation behavior of these gaseous mixtures.     

Mass spectrometric measurements of fractional ion abundances in the stratosphere—Negative ions

Fractional abundances of stratospheric negative ions are for the first time explicitly reported. The measurements made by balloon-borne ion mass spectrometers also rely on recent studies of electric field induced collisional dissociation of negative cluster ions conducted at our laboratory. These indicate that the negative ion composition measurements around 36 km conducted by our group do not suffer from any significant dissociation. The new composition data support ion identifications NO₃^?(HNO₃)_b and HSO₄^?(H₂SO₄)_c(HNO₃)_d and the underlying ion reactions propo previously. Moreover, it is found that HSO₄^?(H₂SO₄)_g-ions appear to be particularly stable and that H₂SO₄-association is very fast. Implications of the ion composition data for ion processes are discussed.     

Stratospheric negative ions—detailed height profiles

Balloon-borne mass spectrometers with extended mass range have been flown during controlled descents. This gave detailed height profiles of stratospheric negative ions between 15 and 34 km. The main ion families were HSO₄^?(H₂SO₄)_m(HNO₃)_n and NO₃^? (HNO₃)_n Information concerning trace gases is o well as an assessment of the problems of ion fragmentation and contamination. Finally, the data are used to derive information concerning the rate of H₂SO₄ clustering.     

Radiolysis of sulfuric acid, sulfuric acid monohydrate, and sulfuric acid tetrahydrate and its relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H₂SO₄), sulfuric acid monohydrate (H₂SO₄·H₂O), and sulfuric acid tetrahydrate (H₂SO₄·4H₂O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H₂O, SO₂, (S₂O₃)_x, H₃O⁺, , and . At high radiation doses, we find that H₂SO₄ molecules are destroyed completely and that H₂SO₄·H₂O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H₂SO₄, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H₂SO₄ or H₂SO₄·H₂O, the loss of H₂SO₄·4H₂O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa’s surface, we speculate that the variations in SO₂ concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.     

Laboratory measurements of the microwave opacity and vapor pressure of sulfuric acid vapor under simulated conditions for the middle atmosphere of Venus

Microwave absorption observed in the 35- to 48-km-altitude region of the Venus atmosphere has been attributed to the presence of gaseous sulfuric acid (H₂SO₄) in that region. This has motivated the laboratory measurement of the microwave absorption at 13.4- and 3.6-cm wavelengths from gaseous H₂SO₄ in a CO₂ atmosphere under simulated conditions for that region. As part of the same experiments, upper limits on the saturation vapor pressure of gaseous H₂SO₄ have also been determined. The measurements for microwave absorption have been made in the 1- to 6-atm pressure range, with temperatures in the 500 to 575°K range. Using a theoretically derived temperature dependence, the best-fit expression for absorption from gaseous H₂SO₄ in a CO₂ atmosphere at the 13.4-cm wavelength is $\text{9.0 × 10}{}^9\text{q(P)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{T}{}^{\mathrm{?3}}\text{(}\text{dB km}{}^{\mathrm{?1}}\text{),}\text{where}\text{q}$ is the H₂SO₄ number mixing ratio, P is the pressure in atmospheres, and T is the temperature in degrees Kelvins. The best-fit expression for absorption at the 3.6-cm wavelength is 4.52 × 10¹⁰q(P)^0.85T^?3 (dB km^?1). The inferred H₂SO₄ vapor pressure above liquid H₂SO₄ corresponds to ln p = 8.84 ? 7220/t where p is the H₂SO₄ vapor pressure (in atm) and T is the temperature in degrees Kelvins. These results suggest that abundances of gaseous H₂SO₄ on the order of 15 to 30 ppm could account for the microwave absorption observed by radio occultation experiments at 13.3- and 3.6-cm wavelengths. They also suggest that such abundances would correspond to saturation vapor pressure existing at or above the 46- to 48-km range, which correlates with the observed cloud base. It is suggested that future measurements of absorption in the 1- to 3-cm wavelength range will provide additional tools for monitoring variations in H₂SO₄ abundance via radio occultation and radio astronomical observations.     

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.     

Aircraft observations of Venus' near-infrared reflection spectrum: Implications for cloud composition

We have obtained measurements of Venus' reflection spectrum in the 1.2 to 4.1-μm spectral region from a NASA-Ames operated Lear jet. This was accomplished by observing both Venus and the sun with a spectrometer that contained a circular, variable interference filter, whose effective spectral resolution was 2%. The aircraft results were compared with computer generated spectra of a number of cloud candidates. The only substance which gave an acceptable match to the profile of Venus' strong 3-μm absorption feature, was a water solution of sulfuric acid, that had a concentration of 75% or more H₂SO₄ by weight. However, our spectra also show a modest decline in reflectivity from 2.3 μm towards 1.2-μm wavekength, which is inconsistent with the flat spectrum of sulfuric acid in this spectral region. We hypothesize that this decline is due to impurities in the sulfuric acid droplets.We also compared our list of cloud candidates with several other observed properties of the Venus clouds. While this comparison does not provide as unique an answer as did our analysis of the 3-μm band, we find that, in agreement with the results of Young (1973) and Sill (1973), concentrated sulfuric acid solutions are compatible with these additional observed properties of the Venus clouds. We conclude that the visible cloud layer of Venus is composed of sulfuric acid solution droplets, whose concentration is 75% H₂SO₄, or greater, by weight.     

Oxidation state of the atmosphere and crust of Venus from pioneer Venus results

Recent spacecraft observations of Venus permit a detailed model of sulfur chemistry in the atmosphere-lithosphere system. Pioneer Venus experiments confirm that, as predicted, COS and H₂S are dominant over SO₂ in the lower atmosphere, and that the equilibrium concentrations of S₂ and S₃ are significant. Many criteria serve to bracket the oxidation state of the crust: it is nearly certain that the S₂^2?/SO₄^2? buffer regulates the oxygen fucagity, and that FeO is at least as abundant as Fe₂O₃ in crustal silicates. A highly oxidized crust (as, for example, would result from O₂ absorption complementary to escape of vast amounts of H₂) is incompatible with the gas-phase sulfur chemistry. If the Pioneer Venus mass spectrometer estimates of the abundance of sulfur gases are correct, Earth-like models for the bulk composition of Venus are seriously in error, and a far lower FeO content is required for Venus.     

Properties of the clouds of Venus,as inferred from airborne observations of its near-infrared reflectivity spectrum

We have measured the shape and absolute value of Venus' reflectivity spectrum in the 1.2-to 4.0-μm spectral region with a circular variable filter wheel spectrometer having a spectral resolution of 1.5%. The instrument package was mounted on the 91-cm telescope of NASA Ames Kuiper Airborne Observatory, and the measurements were obtained at an altitude of about 41,000 feet, when Venus had a phase angle of 86°. Comparing these spectra with synthetic spectra generated with a multiple-scattering computer code, we infer a number of properties of the Venus clouds. We obtain strong confirmatory evidence that the clouds are made of a water solution of sulfuric acid in their top unit optical depth and find that the clouds are made of this material down to an optical depth of at least 25. In addition, we determine that the acid concentration is 84 ± 2% H_2SO4 by weight in the top unit optical depth, that the total optical depth of the clouds is 37.5 ± 12.5, and that the cross-sectional weighted mean particle radius lies between 0.5 and 1.4 μm in the top unit optical depth of the clouds. These results have been combined with a recent determination of the location of the clouds' bottom boundary [Marov et al., Cosmic Res.14, 637–642 (1976)] to infer additional properties about Venus' atmosphere. We find that the average volume mixing ratio of H₂SO₄ and H₂O contained in the cloud material both equal approximately 2× 10^?6. Employing vapor pressure arguments, we show that the acid concentration equals 84 ± 6% at the cloud bottom and that the water vapor mixing ratio beneath the clouds lies between 6 × 10^?4 and 10^?2.