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.     

The composition of the atmosphere of Venus below 100 km altitude: An overview

We review the progress in our understanding of the composition of the Venus atmosphere since the publication of the COSPAR Venus International Reference Atmosphere volume in 1985. Results presented there were derived from data compiled in 1982–1983. More recent progress has resulted in large part from Earth-based studies of the near-infrared radiation from the nightside of the planet. These observations allow us to probe the atmosphere between the cloud tops and the surface. Additional insight has been gained through: (i) the analysis of ultraviolet radiation by satellites and rockets; (ii) data collected by the Vega 1 and 2 landers; (iii) complementary analyses of Venera 15 and 16 data; (iv) ground-based and Magellan radio occultation measurements, and (v) re-analyses of some spacecraft measurements made before 1983, in particular the Pioneer Venus and Venera 11, 13 and 14 data. These new data, and re-interpretations of older data, provide a much better knowledge of the vertical profile of water vapor, and more information on sulfur species above and below the clouds, including firm detections of OCS and SO. In addition, some spatial and/or temporal variations have been observed for CO, H₂O, H₂SO₄, SO₂, and OCS. New values of the D/H ratio have also been obtained.     

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.     

Venus: A perspective at the beginning of planetary exploration

In situ measurements of the Venus atmosphere, made by the entry probes Venera 4, 5, 6, and 7, and data from the Mariner 5 flyby, have provided essentially new and reliable information and have powerfully contributed to our understanding of the nearest planet. The abundances of the principal atmospheric constituents and the temperature and pressure profiles down to the Venus surface were obtained for the first time. It was shown that the atmosphere is composed primarily of CO₂ and that N₂ (if any) and H₂O are relatively minor admixtures. In the region of the Venera 7 landing, the temperature and pressure at the Venus surface were established as equal to 747 ± 20°K and 90 ± 15 kgcm⁻². Space vehicles have also provided limited but quite important information on the physical properties of the Venus upper atmosphere and ionosphere, and on the interaction of the planet with the interplanetary environment. The main characteristics of the Venus atmosphere are discussed here with emphasis on the Venera results, including instrumentation, data processing, and altitude profiles.     

Evidence for a low-altitude origin of lightning on Venus

Radio emissions attributed to lightning on Venus have been recorded by Venera 11 and 12 and by the Pioneer Venus Orbiter. The Venera descent records are compared to patterns of radio propagation within the Venusian atmosphere and an explanation is found for some timing trends that, if correct, indicates the lightning was below 33 km in altitude.     

The clouds of Venus: Sulfuric acid by the lead chamber process

The Pioneer Venus atmospheric probe provided new data on the louds of Venus. A model consistent with this data involves SO₂ being oxidized to H₂SO₄ by NO_x in the presence of H₂O. NO_x also forms nitrosylsulfuric acid (NOHSO₄) dissolved in the H₂SO₄ droplets. This acid solution, along with SO₂ and perhaps NO₂, can explain the uv and visible reflection spectrum of Venus. In the middle and lower clouds NOHSO₄ forms solid particles.     

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.     

Structure of the Venus mesosphere and lower thermosphere from measurements during entry of the pioneer Venus probes

Data on the thermal structure of the nightside middle atmosphere of Venus, from 84 to 137 km altitude, have been obtained from analysis of deceleration measurements from the third Pioneer Venus small probe, the night probe, which entered the atmosphere near the midnight meridian at 27°S latitude. Comparison of the midnight sounding with the morning sounding at 31°S latitude indicates that the temperature structure is essentially diurnally invariant up to 100 km, above which the nightside structure diverges sharply from the dayside toward lower temperatures. Very large diurnal pressure differences develop above 100 km with dayside pressure ten times that on the nightside at 126 km altitude. This has major implications for upper atmospheric dynamics. The data are compared with the measurements of G. M. Keating, J. Y. Nicholson, and L. R. Lake (1980, J. Geophys. Res., 85, 7941–7956) above 140 km with theoretical thermal structure models of Dickinson, and with data obtained by Russian Venera spacecraft below 100 km. Midnight temperatures are ～ 130°K, somewhat warmer than those reported by Keating et al.     

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.     

Solar wind origin of 36Ar on Venus

A hypothesis is considered in which the ³⁶Ar found on Venus is of solar origin. This possibility is quantitatively discussed within the framework of present theories of planetary accumulation by sweep up of planetesimals under gas-free conditions. Solar wind implantation of ³⁶Ar would take place by irradiation of accumulating material during the first ≈10⁵ years of planetary growth, provided that the flux of solar wind was enhanced by a factor of ≈100 at that time. Enrichment of Venus in implanted gas would be a consequence of the irradiated material being initially confined to the innermost edge of the radially opaque circusolar planetesimal disk predicted by these theories. The observed atmospheric data require a Ne/Ar fractionation by a factor of ≈100 during the planetesimal stage. It is also necessary that there be very little mixing of irradiated planetesimals from the inner edge of disk to the distance (≈1 AU) at which the Earth formed. The hypothesis can be tested by measurement of the abundance of Kr and Xe in the Venus atmosphere. Venera data indicate a terrestrial ³⁶Ar/Kr ratio, in disagreement with the solar wind hypothesis. In contrast, the Pioneer experiments find a lower limit to this ratio, well above the terrestrial value, that is compatible with the hypothesis. These experiments also show that Venus' ³⁶Ar/Xe ratio does not correspond to the so-called “planetary” trapped inert gas composition. The inert of Venus could be related to result of admixture of gas with solar composition. The inert gas on Venus could be related to that found in enstatite chondrites.     

Temperature structure in the lower atmosphere of Venus: New results derived from pioneer Venus entry probe measurements

The interpretation of unexpected characteristics of Pioneer Venus temperature measurements, and of the large difference between these and the Venera results, is aided by new Venus temperature profiles derived from engineering measurements of the Pioneer Venus Small-Probe Net Flux Radiometer (SNFR) instruments. To facilitate correction of a temperature-dependent radiometric response, these instruments monitored the temperatures of their deployed radiation detectors. The accurate calibration of the temperature sensors, and their strong thermal coupling to the atmosphere, make it possible to deduce atmospheric temperatures within 2°K (at most altitudes) using a simple two-component thermal model to account for lag effects. These independent temperature profiles generally confirm to high accuracy, the small-probe results of A. Seiff, D. B. Kirk, R. E. Young, R. C. Blanchard, J. T. Findlay, G. M. Kelly, and S. C. Sommer (1980a, J. Geophys. Res.85, pp. 7903–7933) concerning vertical structure and horizontal contrast in the lower atmosphere, although the stable layer below 25 km is found to be slightly more stable (by about 0.4°K/km) and absolute temperatures are an average of 2°K higher. The measured Day-Night thermal contrast is compatible with predicted responses to the diurnal variation in solar heating, except near the cloud base, where 3–5°K differences may be due to thermal radiative heating differences associated with different cloud opacities. Temperature contrasts between latitudes 30 and 60° are roughly consistent with cyclostrophic balance. But pressure and temperature measurements by the Pioneer Venus Sounder probe at 4° latitude, when compared to Small-probe results, imply unreasonably large equatorward accelerations of 100 (m/sec)/day. Poleward accelerations compatible with cyclostrophic balance can be obtained if Sounder-probe temperatures are increased by a scale-factor correction reaching 6–7°K at 13 km.     

On the wind-velocity measurements from Venera spacecraft data

Some features of the wind-velocity determination based on the results of Doppler shift measurements from the Venera probes during their descent in the Venus atmosphere are discussed. The validity of assumptions used in the reduction and analysis of these data are treated in connection with the preceding paper by Ainsworth and Herman. We conclude that the Venera velocity profiles are a valid representation of Venus atmospheric conditions.     

A photochemical model for the Venus atmosphere at 47–112 km

The model is intended to respond to the recent findings in the Venus atmosphere from the Venus Express and ground-based submillimeter and infrared observations. It extends down to 47 km for comparison with the kinetic model for the lower atmosphere (Krasnopolsky, V.A. [2007]. Icarus 191, 25–37) and to use its results as the boundary conditions. The model numerical accuracy is significantly improved by reduction of the altitude step from 2 km in the previous models to 0.5 km. Effects of the NUV absorber are approximated using the detailed photometric observations at 365 nm from Venera 14. The H₂O profile is not fixed but calculated in the model. The model involves odd nitrogen and OCS chemistries based on the detected NO and OCS abundances. The number of the reactions is significantly reduced by removing of unimportant processes. Column rates for all reactions are given, and balances of production and loss may be analyzed in detail for each species.The calculated vertical profiles of CO, H₂O, HCl, SO₂, SO, OCS and of the O₂ dayglow at 1.27 μm generally agree with the existing observational data; some differences are briefly discussed. The OH dayglow is ～30 kR, brighter than the OH nightglow by a factor of 4. The H + O₃ process dominates in the nightglow excitation and O + HO₂ in the dayglow, because of the reduction of ozone by photolysis. A key feature of Venus’ photochemistry is the formation of sulfuric acid in a narrow layer near the cloud tops that greatly reduces abundances of SO₂ and H₂O above the clouds. Delivery of SO₂ and H₂O through this bottleneck determines the chemistry and its variations above the clouds. Small variations of eddy diffusion near 60 km result in variations of SO₂, SO, and OCS at and above 70 km within a factor of ～30. Variations of the SO₂/H₂O ratio at the lower boundary have similar but weaker effect: the variations within a factor of ～4 are induced by changes of SO₂/H₂O by ±5%. Therefore the observed variations of the mesospheric composition originate from minor variations of the atmospheric dynamics near the cloud layer and do not require volcanism. NO cycles are responsible for production of a quarter of O₂, SO₂, and Cl₂ in the atmosphere. A net effect of photochemistry in the middle atmosphere is the consumption of CO₂, SO₂, and HCl from and return of CO, H₂SO₄, and SO₂Cl₂ to the lower atmosphere. These processes may be balanced by thermochemistry in the lower atmosphere even without outgassing from the interior, though the latter is not ruled out by our models. Some differences between the model and observations and the previous models are briefly discussed.     

The modeling of Venus' degassing in terms of K-Ar system

In terms of Ozima's model of argon degassing the Venus' model is presented based on Pioneer Venus and Venera space mission atmospheric composition data. The geochemical conclusions are obtained as following: the Venus' crust is presumably basaltic with potassium content lower than 0.5%; the exterior nonradiogenic³⁶Ar contribution to the total argon inventory is estimated as at least 95%; almost complete argon degassing in the first 0.5 m.y. is supposed. The model is in agreement only with low volcanic productivity on Venus (<5 km³ yr^–1).This value is consistent with the assumption on the lithospheric conductivity as a dominating contribution to the heat losses of Venus' interior in contrast to the hot spot mechanism.     

Limits on Venus' SO2 abundance profile from interferometric observations at 3.4 mm wavelength

The role of SO₂ in the chemistry of the clouds of Venus has been investigated by deducing its mixing ratio profile in the atmosphere through millimeter wavelength interferometric measurements of the planet's limb darkening. The first zero crossing of the Venus visibility function was measured to be β₀ = 0.6221 ± 0.0007 at a wavelength of 3.4 mm using a reference radius for Venus of 6100 km. This measurement constrains the amount of limb darkening and shows that the high concentrations of SO₂ found in the lower atmosphere do not persist above an altitude of 42 km. Thus, a sink for SO₂ exists below the level of the lowest cloud deck.     

Climate control on Venus: Comparison of the carbonate and pyrite models

We review two models describing the Venus climate system: the carbonate and pyrite models. It has been argued carbonate and pyrite are potentially important minerals controlling the climate of Venus, though existence of either minerals has not been confirmed. Although it used to be proposed that carbonation reaction might explain the Venus’ atmospheric CO₂ abundance, it is unlikely Venus’ surface is reactive enough to control the Venus’ massive CO₂ atmosphere. Venus’ surface carbonate is also able to affect the climate through the reaction with atmospheric SO₂ to form anhydrite. Under the carbonate model the climate state is not in equilibrium and would be unstable due to the reaction between carbonate and SO₂. On the other hand, pyrite-magnetite reaction is proposed to explain the Venus’ atmospheric SO₂ abundance. Under pyrite-magnetite reaction, however, the climate would be stabilized such that the existing climate state is maintained over a geological timescale, while some observational facts such as atmospheric abundance of SO₂ and surface temperature could also be reasonably explained.     

Acoustic-gravity waves in the thermosphere of Venus

Properties of acoustic-gravity waves in the upper atmosphere of Venus are studied using a two-fluid model which includes the effects of wave-induced diffusion in a diffusively separated atmosphere. In conjunction with neutral mass spectrometer data from the Pioneer Venus orbiter, the theory should provide information on the distribution of wave sources in the Venus upper atmosphere. Observed wave structure in species density measurements should generally have periods ?30–35 min, small N₂, CO, and O amplitudes, and highly variable phase shifts relative to CO₂. A near resonance may exist between downward phase-propagating internal gravity and diffusion waves near the 165-km level at periods near 29 min. As a result, if very large He wave amplitudes are observed near this level, it will indicate that the wave source is below the 150- to 175-km level and that the exospheric temperature is close to 350°K. Wave energy dissipation may be an important mechanism for heating of the nightside Venus thermosphere. Large-density oscillations in stratospheric cloud layer constituents are also possible and may be detectable by the Pioneer Venus large probe neutral mass spectrometer.     

Large,solid particles in the clouds of Venus: Do they exist?

The discovery of large, solid particles in the clouds of Venus is one of the most significant findings of Pioneer Venus because it means that a substantial mass of the clouds is composed of a material other than sulfuric acid. The evidence which suggests that solid particles form a distinctive size mode is reexamined. The mode is defined by a discontinuity between two size ranges of the Pioneer Venus particle size spectrometer. This discontinuity could represent a real size mode. However, it could also be an artifact of the measurement technique. R. G. Knollenberg (1984) discusses several possible instrumental effects which might have caused this discontinuity. It is hypothesized herein that such effects did occur and that the large particles are really the tail of the mode 2 sulfuric acid particle size distribution and are not a separate mode of solid particles. Using such a revised size distribution, it is shown that all of the Pioneer Venus and Venera optical data from the lower clouds can be explained with sulfuric acid droplets without introducing any solid particles. As a by-product of this analysis, it is also found that the upper clouds of Venus must contain a material with a higher refractive index than sulfuric acid. A small quantity of sulfur could account for this observation.     

Loss of water from Venus. I. Hydrodynamic escape of hydrogen

A one-dimensional photochemical-dynamic model is used to study hydrodynamic loss of hydrogen from a primitive, water-rich atmosphere on Venus. The escape flux is calculated as a function of the H₂O mixing ratio at the atmospheric cold trap. The cold-trap mixing ratio is then related in an approximate fashion to the H₂O concentration in the lower atmosphere. Hydrodynamic escape should have been the dominant loss process for hydrogen when the H₂O mass mixing ratio in the lower atmosphere exceeded ～0.1. The escape rate would have depended upon the magnitude of the solar ultraviolet flux and the atmospheric euv heating efficiency and, to a lesser extent, on the O₂ content of the atmosphere. The time required for Venus to have lost the bulk of a terrestrial ocean of water is on the order of a billion years. Deutrium would have been swept away along with hydrogen if the escape rate was high enough, but some D/H enrichment should have occurred as the escape rate slowed down.     

Airborne spectroscopy and spacecraft radiometry of Venus in the far infrared

In March 1979, the spectrum of Venus was recorded in the far infrared from the G.P. Kuiper Airborne Observatory when the planet subtended a phase angle of 62°. The brightness temperature was observed to be 275°K near 110 cm^?1, dropping to 230°K near 270 cm^?1. Radiance calculations, using temperature and cloud structure formation from the Pioneer Venus mission and including gaseous absorption by the collision-induced dipole of CO₂, yield results consistently brighter than the observations. Supplementing the spectral data, Pioneer Venus OIR data at similar phase angles provide the constraint that any additional infrared opacity must be contained in the upper cloud, H₂SO₄ to the Pioneer-measured upper cloud structure serves to reconcile the model spectrum and the observations, but cloud microphysics strongly indicates that such a high particle density haze $\text{(N ? 1.6 × 10}{}^7\text{cm}{}^{\mathrm{?3}}\text{)}$ is implausible. The atmospheric environment is reviewed with regard to the far infrared opacity and possible particle distribution modifications are discussed. We conclude that the most likely possibility for supplementing the far-infrared opacity is a population of large particles $\text{(}\text{r}\text{? 1 μm)}$ in the upper cloud with number densities less than 1 particle cm^?3 which has remained undetected by in situ measurements.