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1.
To determine how active volcanism might affect the standard picture of sulfur dioxide photochemistry on Io, we have developed a one-dimensional atmospheric model in which a variety of sulfur-, oxygen-, sodium-, potassium-, and chlorine-bearing volatiles are volcanically outgassed at Io's surface and then evolve due to photolysis, chemical kinetics, and diffusion. Thermochemical equilibrium calculations in combination with recent observations of gases in the Pele plume are used to help constrain the composition and physical properties of the exsolved volcanic vapors. Both thermochemical equilibrium calculations (Zolotov and Fegley 1999, Icarus141, 40-52) and the Pele plume observations of Spencer et al. (2000; Science288, 1208-1210) suggest that S2 may be a common gas emitted in volcanic eruptions on Io. If so, our photochemical models indicate that the composition of Io's atmosphere could differ significantly from the case of an atmosphere in equilibrium with SO2 frost. The major differences as they relate to oxygen and sulfur species are an increased abundance of S, S2, S3, S4, SO, and S2O and a decreased abundance of O and O2 in the Pele-type volcanic models as compared with frost sublimation models. The high observed SO/SO2 ratio on Io might reflect the importance of a contribution from volcanic SO rather than indicate low eddy diffusion coefficients in Io's atmosphere or low SO “sticking” probabilities at Io's surface; in that case, the SO/SO2 ratio could be temporally and/or spatially variable as volcanic activity fluctuates. Many of the interesting volcanic species (e.g., S2, S3, S4, and S2O) are short lived and will be rapidly destroyed once the volcanic plumes shut off; condensation of these species near the source vent is also likely. The diffuse red deposits associated with active volcanic centers on Io may be caused by S4 radicals that are created and temporarily preserved when sulfur vapor (predominantly S2) condenses around the volcanic vent. Condensation of SO across the surface and, in particular, in the polar regions might also affect the surface spectral properties. We predict that the S/O ratio in the torus and neutral clouds might be correlated with volcanic activity—during periods when volcanic outgassing of S2 (or other molecular sulfur vapors) is prevalent, we would expect the escape of sulfur to be enhanced relative to that of oxygen, and the S/O ratio in the torus and neutral clouds could be correspondingly increased. 相似文献
2.
Observations of the Io plasma torus and neutral clouds indicate that the extended ionian atmosphere must contain sodium, potassium, and chlorine in atomic and/or molecular form. Models that consider sublimation of pure sulfur dioxide frost as the sole mechanism for generating an atmosphere on Io cannot explain the presence of alkali and halogen species in the atmosphere—active volcanoes or surface sputtering must also be considered, or the alkali and halide species must be discharged along with the SO2 as the frost sublimates. To determine how volcanic outgassing can affect the chemistry of Io's atmosphere, we have developed a one-dimensional photochemical model in which active volcanoes release a rich suite of S-, O-, Na-, K-, and Cl-bearing vapor and in which photolysis, chemical reactions, condensation, and vertical eddy and molecular diffusion affect the subsequent evolution of the volcanic gases. Observations of Pele plume constituents, along with thermochemical equilibrium calculations of the composition of volcanic gases exsolved from high-temperature silicate magmas on Io, are used to constrain the composition of the volcanic vapor. We find that NaCl, Na, Cl, KCl, and K will be the dominant alkali and chlorine gases in atmospheres generated from Pele-like plume eruptions on Io. Although the relative abundances of these species will depend on uncertain model parameters and initial conditions, these five species remain dominant for a wide variety of realistic conditions. Other sodium and chlorine molecules such as NaS, NaO, Na2, NaS2, NaO2, NaOS, NaSO2, SCl, ClO, Cl2, S2Cl, and SO2Cl2 will be only minor constituents in the ionian atmosphere because of their low volcanic emission rates and their efficient photochemical destruction mechanisms. Our modeling has implications for the general appearance, properties, and variability of the neutral sodium clouds and jets observed near Io. The neutral NaCl molecules present at high altitudes in atmosph eres generated by active volcanoes might provide the NaX+ ion needed to help explain the morphology of the high-velocity sodium “stream” feature observed near Io. 相似文献
3.
John R. Spencer Emmanuel Lellouch Miguel A. López-Valverde Thomas K. Greathouse Jean-Marie Flaud 《Icarus》2005,176(2):283-304
We have observed about 16 absorption lines of the ν2 SO2 vibrational band on Io, in disk-integrated 19-μm spectra taken with the TEXES high spectral resolution mid-infrared spectrograph at the NASA Infrared Telescope Facility in November 2001, December 2002, and January 2004. These are the first ground-based infrared observations of Io's sunlit atmosphere, and provide a new window on the atmosphere that allows better longitudinal and temporal monitoring than previous techniques. Dramatic variations in band strength with longitude are seen that are stable over at least a 2 year period. The depth of the strongest feature, a blend of lines centered at 530.42 cm−1, varies from about 7% near longitude 180° to about 1% near longitude 315° W, as measured at a spectral resolution of 57,000. Interpretation of the spectra requires modeling of surface temperatures and atmospheric density across Io's disk, and the variation in non-LTE ν2 vibrational temperature with altitude, and depends on the assumed atmospheric and surface temperature structure. About half of Io's 19-μm radiation comes from the Sun-heated surface, and half from volcanic hot spots with temperatures primarily between 150 and 200 K, which occupy about 8% of the surface. The observations are thus weighted towards the atmosphere over these low-temperature hot spots. If we assume that the atmosphere over the hot spots is representative of the atmosphere elsewhere, and that the atmospheric density is a function of latitude, the most plausible interpretation of the data is that the equatorial atmospheric column density varies from about 1.5×1017 cm−2 near longitude 180° W to about 1.5×1016 cm−2 near longitude 300° W, roughly consistent with HST UV spectroscopy and Lyman-α imaging. The inferred atmospheric kinetic temperature is less than about 150 K, at least on the anti-Jupiter hemisphere where the bands are strongest, somewhat colder than inferred from HST UV spectroscopy and millimeter-wavelength spectroscopy. This longitudinal variability in atmospheric density correlates with the longitudinal variability in the abundance of optically thick, near-UV bright SO2 frost. However it is not clear whether the correlation results from volcanic control (regions of large frost abundance result from greater condensation of atmospheric gases supported by more vigorous volcanic activity in these regions) or sublimation control (regions of large frost abundance produce a more extensive atmosphere due to more extensive sublimation). Comparison of data taken in 2001, 2002, and 2004 shows that with the possible exception of longitudes near 180° W between 2001 and 2002, Io's atmospheric density does not appear to decrease as Io recedes from the Sun, as would be expected if the atmosphere were supported by the sublimation of surface frost, suggesting that the atmosphere is dominantly supported by direct volcanic supply rather than by frost sublimation. However, other evidence such as the smooth variation in atmospheric abundance with latitude, and atmospheric changes during eclipse, suggest that sublimation support is more important than volcanic support, leaving the question of the dominant atmospheric support mechanism still unresolved. 相似文献
4.
Using the Hubble Space Telescope's Space Telescope Imaging Spectrograph we have obtained for the first time spatially resolved 2000-3000 Å spectra of Io's Prometheus plume and adjoining regions on Io's anti-jovian hemisphere in the latitude range 60° N-60° S, using a 0.1″ slit centered on Prometheus and tilted roughly 45° to the spin axis. The SO2 column density peaked at 1.25×1017 cm−2 near the equator, with an additional 5×1016 cm−2 enhancement over Prometheus corresponding to a model volcanic SO2 output of 105 kg s−1. Apart from the Prometheus peak, the SO2 column density dropped fairly smoothly away from the subsolar point, even over regions that included potential volcanic sources. At latitudes less than ±30°, the dropoff rate was consistent with control by vapor pressure equilibrium with surface frost with subsolar temperature 117.3±0.6 K, though SO2 abundance was higher than predicted by vapor pressure control at mid-latitudes, especially in the northern hemisphere. We conclude that, at least at low latitudes on the anti-jovian hemisphere where there are extensive deposits of optically-thick SO2 frost, the atmosphere is probably primarily supported by sublimation of surface frost. Although the 45° tilt of our slit prevents us from separating the dependence of atmospheric density on solar zenith angle from its dependence on latitude, the pattern is consistent with a sublimation atmosphere regardless of which parameter is the dominant control. The observed drop in gas abundance towards higher latitudes is consistent with the interpretation of previous Lyman alpha images of Io as indicating an atmosphere concentrated at low latitudes. Comparison with previous disk-resolved UV spectroscopy, Lyman-alpha images, and mid-infrared spectroscopy suggests that Io's atmosphere is denser and more widespread on the anti-jovian hemisphere than at other longitudes. SO2 gas temperatures were in the range of 150-250 K over the majority of the anti-jovian hemisphere, consistent with previous observations. SO was not definitively detected in our spectra, with upper limits to the SO/SO2 ratio in the range 1-10%, roughly consistent with previous observations. S2 gas was not seen anywhere, with an upper limit of 7.5×1014 cm−2 for the Prometheus plume, confirming that this plume is significantly poorer in S2 than the Pele plume (S2 /SO2<0.005, compared to 0.08-0.3 at Pele). In addition to the gas absorption signatures, we have observed continuum emission in the near ultraviolet (near 2800 Å) for the first time. The brightness of the observed emission was directly correlated with the SO2 abundance, strongly peaking in the equatorial region over Prometheus. Emission brightness was modestly anti-correlated with the jovian magnetic latitude, decreasing when Io intersected the torus centrifugal equator. 相似文献
5.
An extensive set of HI Lyman-α images obtained with the Hubble Space Telescope (HST) Space Telescope Imaging Spectrograph (STIS) from 1997-2001 has been analyzed to provide information about the spatial and temporal character of Io's SO2 atmosphere. An atmospheric distribution map derived from the observations reveals that the sunlit SO2 atmosphere is temporally stable on a global scale, with only small local changes. An anti-/sub-jovian asymmetry in the SO2 distribution is present in all 5 years of the observations. The average daytime atmosphere is densest on the anti-jovian hemisphere in the equatorial regions, with a maximum equatorial column density of 5.0×1016 cm−2 at 140° longitude. The SO2 atmosphere also has greater latitudinal extent on the anti-jovian hemisphere as compared to the sub-jovian. The atmospheric distribution appears to be best correlated with the location of hot spots and known volcanic plumes, although small number statistics for the plumes limits the correlation. 相似文献
6.
We present an updated model for the photochemistry of Io's atmosphere and ionosphere and use this model to investigate the sensitivity of the chemical structure to vertical transport rates. SO2is assumed to be the dominant atmospheric gas, with minor molecular sodium species such as Na2S or Na2O released by sputtering or venting from the surface. Photochemical products include SO, O2, S, O, Na, NaO, NaS, and Na2. We consider both “thick” and “thin” SO2atmospheres that encompass the range allowed by recent HST and millimeter-wave observations, and evaluate the possibility that O2and/or SO may be significant minor dayside constituents and therefore likely dominant nightside gases. The fast reaction between S and O2limits the column abundance of O2to ∼104less than that calculated by Kumar (J. Geophys. Res.87, 1677–1684, 1982; 89(A9), 7399–7406, 1984) for a pure sulfur/oxygen atmosphere. If a significant source of NaO2or Na2O were supplied by the surface and mixed rapidly upward, then oxygen liberated in the chemical reactions which also liberate free Na would provide an additional source of O2. Fast eddy mixing will enhance the transport of molecular sodium species to the exobase, in addition to increasing the vertical transport rate of ions. Ions produced in the atmosphere will be accelerated by the reduced corotation electric field penetrating the atmosphere. These ions experience collisions with the neutral gas, leading to enhanced vertical ion diffusion. The dominant ion, Na+, is lost primarily by charge exchange with Na2O and/or Na2S in the lower atmosphere and by diffusion through the ionopause in the upper atmosphere. The atmospheric column abundance of SO, O2, and the upper atmosphere escape rates of Na, S, O, and molecular sodium species are all strong functions of the eddy mixing rate. Most atmospheric escape, including that of molecular sodium species, probably occurs from the low density “background” SO2atmosphere, while a localized high density “volcanic” SO2atmosphere can yield an ionosphere consistent with that detected by the Pioneer 10 spacecraft. 相似文献
7.
Sergey L. Gratiy Andrew C. Walker David B. Goldstein Laurence M. Trafton 《Icarus》2010,207(1):394-408
Conflicting observations regarding the dominance of either sublimation or volcanism as the source of the atmosphere on Io and disparate reports on the extent of its spatial distribution and the absolute column abundance invite the development of detailed computational models capable of improving our understanding of Io’s unique atmospheric structure and origin. Improving upon previous models, Walker et al. (Walker, A.C., Gratiy, S.L., Levin, D.A., Goldstein, D.B., Varghese, P.L., Trafton, L.M., Moore, C.H., Stewart, B. [2009]. Icarus) developed a fully 3-D global rarefied gas dynamics model of Io’s atmosphere including both sublimation and volcanic sources of SO2 gas. The fidelity of the model is tested by simulating remote observations at selected wavelength bands and comparing them to the corresponding astronomical observations of Io’s atmosphere. The simulations are performed with a new 3-D spherical-shell radiative transfer code utilizing a backward Monte Carlo method. We present: (1) simulations of the mid-infrared disk-integrated spectra of Io’s sunlit hemisphere at 19 μm, obtained with TEXES during 2001-2004; (2) simulations of disk-resolved images at Lyman-α obtained with the Hubble Space Telescope (HST), Space Telescope Imaging Spectrograph (STIS) during 1997-2001; and (3) disk-integrated simulations of emission line profiles in the millimeter wavelength range obtained with the IRAM-30 m telescope in October-November 1999. We found that the atmospheric model generally reproduces the longitudinal variation in band depth from the mid-infrared data; however, the best match is obtained when our simulation results are shifted ∼30° toward lower orbital longitudes. The simulations of Lyman-α images do not reproduce the mid-to-high latitude bright patches seen in the observations, suggesting that the model atmosphere sustains columns that are too high at those latitudes. The simulations of emission line profiles in the millimeter spectral region support the hypothesis that the atmospheric dynamics favorably explains the observed line widths, which are too wide to be formed by thermal Doppler broadening alone. 相似文献
8.
Two-dimensional model calculations (altitude and solar zenith angle) are performed to investigate the impact of electron chemistry on the composition and structure of Io's atmosphere. The calculations are based upon the model of Wong and Smyth (2000, Icarus 146, 60-74) for Io's SO2 sublimation atmosphere with the addition of new electron chemistry, where the interactions of the electrons and neutrals are treated in a simple fashion. The model calculations are presented for Io's atmosphere at western elongation (dusk ansa) for both a low-density case (subsolar temperature of 113 K) and a high-density case (subsolar temperature of 120 K). The impact of electron-neutral chemistry on the composition and structure of Io's atmosphere is confined primarily to an interaction layer. The penetration depth of the interaction layer is limited to high altitudes in the thicker dayside atmosphere but reaches the surface in the thinner dayside and/or nightside atmosphere at larger solar zenith angles. Within most of the thicker dayside atmosphere, the column density of SO2 is not significantly altered by electrons, but in the interaction layer all number densities are significantly altered: SO2 is reduced, O, SO, S, and O2 are greatly enhanced, and O, SO, and S become comparable to SO2 at high altitudes. For the thinner nightside atmosphere, the species number densities are dramatically altered: SO2 is drastically reduced to the least abundant species of the SO2 family, SO and O2 are significantly reduced at all altitudes, and O and S are dramatically enhanced and become the dominant species at all altitudes except near the surface. The interaction layer also defines the location of the emission layer for neutrals excited by electron impact and hence determines the fraction of the total neutral column density that is visible in remote observation. Electron chemistry may also impact the ratio of the equatorial to polar SO2 column density deduced from Lyman-α images and the north-south alternating and System III longitude-dependent asymmetry observed in polar O and S emissions. 相似文献
9.
Chemical kinetic model for the lower atmosphere of Venus 总被引：1，自引：0，他引：1
Vladimir A. Krasnopolsky 《Icarus》2007,191(1):25-37
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, Sx), thermochemistry in the lowest 10 km, and photolysis of S3. The sulfur bonds in OCS and Sx 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 Sx, and a minor photochemical cycle which forms CO and Sx from OCS. The net effect of thermochemistry in the lowest 10 km is formation of OCS from CO and Sx. 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 Sx. The geological cycle of sulfur remains unchanged. 相似文献
10.
A 1-D collisional Monte Carlo model of Europa's atmosphere is described in which the sublimation and sputtering sources of H2O molecules and their molecular fragments are accounted for as well as the radiolytically produced O2. Dissociation and ionization of H2O and O2 by magnetospheric electron, solar UV-photon and photo-electron impact, and collisional ejection from the atmosphere by the low-energy plasma are taken into account. Reactions with the surface are discussed, but only adsorption and atomic oxygen recombination are included in this model. The size of the surface-bounded oxygen atmosphere of Europa is primarily determined by a balance between atmospheric sources from irradiation of the satellite's icy surface by the high-energy magnetospheric charged particles and atmospheric losses from collisional ejection by the low-energy plasma, photo- and electron-impact dissociation, and ionization and pick-up from the surface-bounded atmosphere. A range of sources rates for O2 to H2O are used with a larger oxygen-to-water ratio than suggested by laboratory measurements in order to account for differences in adsorption onto grains in the regolith. These calculations show that the atmospheric composition is determined by both the water and oxygen photochemistry in the near-surface region, escape of suprathermal oxygen and water into the jovian system, and the exchange of radiolytic water products with the porous regolith. For the electron impact ionization rates used, pick-up ionization is the dominant oxygen loss process, whereas photo-dissociation and atmospheric sputtering are the dominant sources of neutral oxygen for Europa's neutral torus. Including desorption and loss of water enhances the supply of oxygen species to the neutral torus, but hydrogen produced by radiolysis is the dominant source of neutrals for Europa's torus in these models. 相似文献
11.
Silicon tetrafluoride (SiF4) is observed in terrestrial volcanic gases and is predicted to be the major F-bearing species in low-temperature volcanic gases on Io [Schaefer, L., Fegley Jr., B., 2005b. Alkali and halogen chemistry in volcanic gases on Io. Icarus 173, 454-468]. SiF4 gas is also a potential indicator of silica-rich crust on Io. We used F/S ratios in terrestrial and extraterrestrial basalts, and gas/lava enrichment factors for F and S measured at terrestrial volcanoes to calculate equilibrium SiF4/SO2 ratios in volcanic gases on Io. We conclude that SiF4 can be produced at levels comparable to the observed NaCl/SO2 gas ratio. We also considered potential loss processes for SiF4 in volcanic plumes and in Io's atmosphere including ion-molecule reactions, electron chemistry, photochemistry, reactions with the major atmospheric constituents, and condensation. Photochemical destruction (tchem ∼266 days) and/or condensation as Na2SiF6 (s) appear to be the major sinks for SiF4. We recommend searching for SiF4 with infrared spectroscopy using its 9.7 μm band as done on Earth. 相似文献
12.
A one-dimensional Direct Simulation Monte Carlo (DSMC) model is used to examine the effects of a non-condensable species on Io's sulfur dioxide sublimation atmosphere during eclipse and just after egress. Since the vapor pressure of SO2 is extremely sensitive to temperature, the frost-supported dayside sublimation atmosphere had generally been expected to collapse during eclipse as the surface temperature dropped. For a pure SO2 atmosphere, however, it was found that during the first 10 min of eclipse, essentially no change in the atmospheric properties occurs at altitudes above ∼100 km due to the finite ballistic/acoustic time. Hence immediately after ingress the auroral emission morphology above 100 km should resemble that of the immediate pre-eclipse state. Furthermore, the collapse dynamics are found to be greatly altered by the presence of even a small amount of a non-condensable species which forms a diffusion layer near the surface that prevents rapid collapse. It is found that after 10 min essentially no collapse has occurred at altitudes above ∼20 km when a nominal mole fraction of non-condensable gas is present. Collapse near the surface occurs relatively quickly until a static diffusion layer many mean free paths thick of the non-condensable gas builds up which then retards further collapse of the SO2 atmosphere. For example, for an initial surface temperature of 110 K and 35% non-condensable mole-fraction, the ratio of the SO2 column density to the initial column density was found to be 0.73 after 10 min, 0.50 after 30 min, and 0.18 at the end of eclipse. However, real gas species (SO, O2) may not be perfectly non-condensable at Io's surface temperatures. If the gas species was even weakly condensable (non-zero sticking/reaction coefficient) then the effect of the diffusion layer on the dynamics was dramatically reduced. In fact, if the sticking coefficient of the non-condensable exceeds ∼0.25, the collapse dynamics are effectively the same as if there were no non-condensable present. This sensitivity results because the loss of non-condensable to the surface reduces the effective diffusion layer size, and the formation of an effective diffusion layer requires that the layer be stationary; this does not occur if the surface is a sink. Upon egress, vertical stratification of the condensable and non-condensable species occurs, with the non-condensable species being lifted (or pushed) to higher altitudes by the sublimating SO2 after the sublimating atmosphere becomes collisional. Stratification should affect the morphology and intensity of auroral glows shortly after egress. 相似文献
13.
First measurements of SO2 and SO in the Venus mesosphere (70-100 km) are reported. This altitude range is distinctly above the ∼60-70 km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO2, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO2 and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO2 and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO2/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO2 and SO at 85-100 km than at 70-85 km. The observed increase of SO2 mixing ratio with altitude requires that the primary SO2 source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO2. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO + SO2) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO2. 相似文献
14.
Vladimir A. Krasnopolsky 《Icarus》2012,218(1):230-246
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. 相似文献
15.
Constantine C.C. Tsang John R. Spencer Emmanuel Lellouch Miguel A. López-Valverde Matthew J. Richter Thomas K. Greathouse 《Icarus》2012,217(1):277-296
We present an analysis of 19 μm spectra of Io’s SO2 atmosphere from the TEXES mid-infrared high spectral resolution spectrograph on NASA’s Infrared Telescope Facility, incorporating new data taken between January 2005 and June 2010 and a re-analysis of earlier data taken from November 2001 to January 2004. This is the longest set of contiguous observations of Io’s atmosphere using the same instrument and technique thus far. We have fitted all 16 detected blended absorption lines of the ν2 SO2 vibrational band to retrieve the subsolar values of SO2 column abundance and the gas kinetic temperature. By incorporating an existing model of Io’s surface temperatures and atmosphere, we retrieve sub-solar column densities from the disk-integrated data. Spectra from all years are best fit by atmospheric temperatures <150 K. Best-fit gas kinetic temperatures on the anti-Jupiter hemisphere, where SO2 gas abundance is highest, are low and stable, with a mean of 108 (±18) K. The sub-solar SO2 column density between longitudes of 90–220° varies from a low of 0.61 (±0.145) × 10?17 cm?2, near aphelion in 2004, to a high of 1.51 (±0.215) × 1017 cm?2 in 2010 when Jupiter was approaching its early 2011 perihelion. No correlation in the gas temperature was seen with the increasing SO2 column densities outside the errors.Assuming that any volcanic component of the atmosphere is constant with time, the correlation of increasing SO2 abundance with decreasing heliocentric distance provides good evidence that the atmosphere is at least partially supported by frost sublimation. The SO2 frost thermal inertias and albedos that fit the variation in atmospheric density best are between 150–1250 W m?2 s?1/2 K?1 and 0.613–0.425 respectively. Photometric evidence favors albedos near the upper end of this range, corresponding to thermal inertias near the lower end. This relatively low frost thermal inertia produces larger amplitude seasonal variations than are observed, which in turn implies a substantial additional volcanic atmospheric component to moderate the amplitude of the seasonal variations of the total atmosphere on the anti-Jupiter hemisphere. The seasonal thermal inertia we measure is unique both because it refers exclusively to the SO2 frost surface component, and also because it refers to relatively deep subsurface layers (few meters) due to the timescales of many years, while previous studies have determined thermal inertias at shallower levels (few centimeters), relevant for timescales of ～2 h (eclipse) or ～2 days (diurnal curves). 相似文献
16.
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 OO bond is broken mainly by S + O2 and SO + HO2. In the low-H2 models additional reactions for breaking the OO 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 NOx 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. 相似文献
17.
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. 相似文献
18.
Laura Schaefer 《Icarus》2005,173(2):454-468
We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10−6 to 10+1 bars) ranges, which overlap the nominal conditions at Pele (T=1760 K, P=0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. The elemental abundances for O, S, Na, K, and Cl are based upon observations. CI chondritic elemental abundances relative to sulfur are used for the other alkalis and halogens (as yet unobserved on Io). We predict the major alkali species in Pele-like volcanic gases and the percentage distribution of each alkali are LiCl (73%), LiF (27%); NaCl (81%), Na (16%), NaF (3%); KCl (91%), K (5%), KF (4%); RbCl (93%), Rb (4%), RbF (3%); CsCl (92%), CsF (6%), Cs (2%). Likewise the major halogen species and the percentage distribution of each halogen are NaF (88%), KF (10%), LiF (2%); NaCl (89%), KCl (11%); NaBr (89%), KBr (10%), Br (1%); NaI (61%), I (30%), KI (9%). We predict the major halogen condensates and their condensation temperatures at P=0.01 bar are NaF (1115 K), LiF (970 K); NaCl (1050 K), KCl (950 K); KBr (750 K), RbBr (730 K), CsBr (645 K); and solid I2 (200 K). We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. Their estimated photochemical lifetimes range from a few minutes for alkali iodides to a few hours for alkali fluorides. Condensation is apparently the only loss process for elemental iodine. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observations of brown dwarfs we also recommend a search of Io's extended atmosphere and the Io plasma torus for neutral and ionized Li, Cs, Rb, and F. 相似文献
19.
Vladimir A. Krasnopolsky 《Icarus》2011,215(1):197-203
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 SOX), 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 SOX at 70-110 km are briefly discussed and some weaknesses are outlined. The possible source of high altitude SOX on Venus remains unclear and probably does not exist. 相似文献
20.
Using Voyager results, we have made crude estimates of the rate at which Io loses volatiles by a variety of processes to the surrounding magnetosphere for both the current SO2-dominated atmosphere as well as hypothetical paleoatmospheres in which other gases, such as N2, may have been the dominant constituent. Loss rates are strongly influenced by the surface pressure on the night side, the relationship between the exobase and the Jovian magnetospheric boundary, the exospheric temperature, and the peak altitudes reached by volcanic plumes. Several mechanisms make significant contributions to the prodigious rate at which Io is currently losing volatiles. These include: interaction of the magnetospheric plasma with volcanic plume particles and the background atmosphere; sputtering of ices on the surface, if the nightside atmospheric pressure is low enough; and Jeans' escape of O, a dissociation product of SO2 gas. For paleoatmospheres, only the first two of these mechanisms would have been effective. However, they are capable of eliminating large amounts of N2 and other volatiles from Io over the satellite's lifetime. Io could have also lost large amounts of water over its lifetime due to the extensive recycling of water between its upper and lower crust, with the partial dissociation of water vapor in silicate magma chambers initiating this loss process. Significant amounts of water may also have been lost as a result of the interaction of the magnetospheric plasma with water ice particles in volcanic plumes. Once an SO2-dominated atmosphere becomes established, much water may have also been lost through the sputtering of surface water ice. 相似文献