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It is argued that photochemical processes, driven by ultraviolet starlight, could lead to large deuterium fractionation for H2O and CH4 relative to H2 in the primitive solar nebula. Implications for deuterium enrichment observed in planetary atmospheres are briefly discussed.
The growth of a permanent, permeable, dust mantle on the surface of a comet nucleus, composed initially of dusty amorphous water ice, is investigated. Numerical simulations of the evolution of one-dimensional comet nucleus models, in Comet Halley's orbit, are carried out for various parameters, allowing for the crystallization of the amorphous ice. It is assumed that the mantle forms gradually, by the accumulation of a constant fraction (0.001-0.01) of the dust, which is not carried away with the sublimating ice. It is found that an approximately 1-cm-thick dust mantle diminishes the average sublimation rate by a factor of approximately 5, and a further growth of the dust mantle may decrease the surface activity of the nucleus by another factor of 10. Therefore, the activity of a dust-covered nucleus is expected to result mainly from exposed patches of ice and from craters, such as were observed on Comet Halley by Giotto. These are formed by explosions of gas-filled pockets in the crystalline outer layer of the nucleus. The insulating effect of the dust mantle causes the crystallization of the amorphous ice to proceed at a slower rate than in the case of a bare icy nucleus. Thus, the thickness of the outer crystalline shell, overlying the amorphous ice core, is always greater than 15 m, but does not exceed a few tens of meters. This size range is compatible with the amount of gas released in the numerous small explosions which were observed on Comet Halley.
It is argued that the formation of the methoxy radical (CH3O) from H + H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe (1977a, J. Chem. Phys. 66, 4745) and transition state theory. We briefly discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv (1975, Icarus 24, 197) and A. Bar-Nun and S. Chang (1983, J. Geophys. Res. 88, 6662) and for organic synthesis in the prebiotic terrestrial atmosphere.
The thick sequences of layered deposits found in the Valles Marineris have recently been determined by S.S. Nedell, S.W. Squyres, and D.W. Andersen (1987, Icarus, 70, 409-441) to contain a minimum of approximately 10(5) km3 of material. We suggest that this material could be derived from the precipitation of 30 mbar of atmospheric CO2 as carbonates in lakes. As surface temperatures fell on Mars, the presence of an insulating ice cover would have allowed liquid water to exist, fed by transitory surface melting. Atmospheric CO2 would have accumulated in such lakes enhancing carbonate precipitation. Support for this hypothesis comes from processes that occur in the perennially frozen lakes in the dry valleys of Antarctica where the mean temperature is 253 degrees K and the lake water is supersaturated with atmospheric gases. A search of the recently reissued Mariner 6/7 infrared spectrometer data in the wavelength region between 2 and 6 micrometers failed to confirm the presence of carbonates. Due to the fact that no spectral footprints appear to directly overlie the layered deposits, and that deposits may be blanketed by an eolian mantle, this negative result is inconclusive. We feel that the canyon deposits are still a prime site for future searches for carbonates on Mars.
The physical and chemical processes that lead to the preferential escape of hydrogen over deuterium in the Martian atmosphere are studied in detail using a one-dimensional photochemical model. Comparison of our theory with recent observations of HDO suggests that, averaged over the planet, Mars contains 0.2 m of crustal water that is exchangeable with the atmosphere. Our estimate is considerably lower than recent estimates of subsurface water on Mars based on geomorphological analysis of Viking images. The estimate can be reconciled if only a small fraction of crustal water can exchange with the atmosphere.
Detailed models of the internal structures of Pluto and Charon, assuming rock and water ice as the only constituents, indicate that the mean silicate mass fraction of this two-body system is on the order of 0.7; thus the Pluto/Charon system is significantly "rockier" than the satellites of the giant planets (silicate mass fraction approximately 0.55). This compositional contrast reflects different formation mechanisms: it is likely that Pluto and Charon formed directly from the solar nebula, while the circumplanetary nebulae that produced the giant planet satellites were derived from envelopes that surrounded the forming giant planets (envelopes in which icy planetesimals dissolved more readily than rocky planetesimals). Simple cosmic abundance calculations, and the assumption that the Pluto/Charon system formed directly from solar nebula condensates, strongly suggest that the majority of the carbon in the outer solar nebula was in the form of carbon monoxide; these results are consistent with (1) inheritance from the dense molecular clouds in the interstellar medium (where CH4/CO < 10(-2) in the gas phase) and/or (2) of the Lewis and Prinn kinetic inhibition model of solar nebula chemistry. Theoretical predictions of the C/H enhancements in the atmospheres of the giant planets, when compared to the actual observed enhancements, suggest that 10%, or slightly more, of the carbon in the outer solar nebula was in the form of condensed materials (although the amount of condensed C may have dropped slightly with increasing heliocentric distance). Strict compositional limits computed for the Pluto/Charon system using the densities of CH4 and CO ices indicate that these pure ices are at best minor components in the interiors of these bodies, and imply that CH4 and CO ices were not the dominant C-bearing solids in the outer nebula. Clathrate-hydrates could not have appropriated enough CH4 or CO to be the major form of condensed carbon, although such clathrates may be necessary to explain the presence of methane on Pluto after its formation from a CO-rich nebula. Laboratory studies of carbonaceous chondrites, and spacecraft observations of Comet Halley, strongly suggest that of the remaining possibilities, organic material, rather than elemental carbon, is the most likely candidate for the dominant C-bearing solid in the outer solar nebula. We conclude that the majority of the carbon in the outer solar nebula was in gaseous CO; 10% to a few tens of percent of the C was in condensed organic materials; and at least a trace amount of carbon was in methane gas.
The majority of the interplanetary dust particles (IDPs) collected in the stratosphere belong to one of three major classes, the first two dominated by the anhydrous minerals olivine and pyroxene, and the third by hydrous layer-lattice silicates. Infrared spectroscopy and transmission electron microscopy studies show that the different IDP classes represent different types of dust that exist as individual particles in interplanetary space. The majority of the collected IDPs smaller than 30 micrometers in diameter in the layer-lattice silicate and pyroxene classes appear not to have been heated to temperatures above 600 degrees C during atmospheric entry. The relatively low maximum temperatures experienced by these IDPs during atmospheric entry imply that they arrive at the top of the atmosphere with low geocentric encounter velocities. This limits the possible encounter trajectories for these particles to relatively circular, prograde orbits. As a result, it is unlikely that these IDPs are from Earth-crossing comets or asteroids. Asteroids, and comets having low inclinations and perihelia outside 1.2 AU, appear to be the best candidates for the parent bodies of the pyroxene and layer-lattice silicate particles. Chemical and mineralogical information suggests that the pyroxene-rich IDPs are from comets and the layer-lattice silicate-rich IDPs are from asteroids. The collected IDPs dominated by olivine appear to include a larger fraction of particles heating above 600 degrees C, suggesting that these particles were captured from more eccentric orbits. This, and the observation of the infrared spectral features of olivine in several comets suggest these particles have a cometary origin. Since much of the collected dust has apparently been captured from nearly circular, prograde orbits and since there are no appropriate parent bodies presently in such orbits, these results provide an experimental confirmation that the Poynting-Robertson effect exists as a nongravitational force important in the orbital evolution of dust in the Solar System.
The properties of the outer layers of comets considered for the future Comet Rendezvous and Asteroid Flyby and Comet Nucleus Sample Return missions are studied, by following numerically the thermal evolution of spherically symmetric models of the nucleus, in the orbit of Comet P/Tempel-1. The evolution starts from isothermal (10 degrees K) and homogeneous nuclei, composed of amorphous ice and dust. The crystallization of amorphous ice at 137 degrees K is taken into account. As the ice sublimates, a permanent dust mantle is allowed to accumulate, at a rate which is proportional to the sublimation rate. Evolutionary sequences are computed for different values of the density, the dust/ice mass ratio, and the (constant) fraction of the dust which is not carried away with the sublimating ice. The main conclusions are (a) the temperatures at the outer and inner surfaces of the dust mantle are not very sensitive to changes in the parameters; (b) although the dust is assumed permeable to water vapor the rate of erosion of the nucleus slows down as the dust mantle grows and its insulating effect increases; (c) the temperature at a depth of 10 m is approximately 160 degrees K for all models considered and hence, the ice at this depth is crystalline; (d) the total thickness of the crystalline ice layer, between the dust mantle and the amorphous ice core, varies from 40 to 240 m, depending on the parameters assumed. Consequently, it should be difficult for the probes of the two comet missions to sample pristine amorphous ice, unless they are aimed at the bottom of an active crater.
The findings of the Giotto and Vega spacecrafts on the gas composition of comet Halley, together with an experimental study on the trapping of gas mixtures in amorphous water ice, enable estimation of the gas composition and temperature in the region of comet Halley's formation: If Halley was formed in the solar nebula by condensation of water vapor in the presence of gas, in the region of its formation the CO/CH4 ratio had to be at least 100 and the temperature about 48 K. The ice particles that formed the comet could not have condensed at a higher temperature and subsequently cool down because then the 7% CO found as a parent molecule could not have been trapped in the ice. A approximately 48 K formation implies that the ice was in amorphous form. This temperature is surprisingly close to the temperatures observed by IRAS for the circumstellar dust shells around alpha PsA (55 K) and epsilon Eri (45 K) and supports the suggestion that short-period comets were formed outside the region of planet formation. The CO content of comet Halley and sensitivity to explosion of irradiated, ice-coated, interstellar grains seem to exclude the possibility of their direct incorporation into comets. Yet, they might have provided the condensed organics--the "CHON" materials.
We have developed a radiative-convective model of the thermal structure of Titan's atmosphere. The model computes the solar and infrared radiation in a series of spectral intervals with vertical resolution. Sources of opacity in the visible and near infrared include stratospheric haze particles, methane cloud particles, and gaseous methane; sources of opacity in the thermal infrared include the pressure-induced opacity of N2, CH4, and H2, the permitted transitions of C2H2 and C2H6, and particulate opacity. The haze properties are determined with a simple microphysics model. The model contains a minimum of free parameters and we try to determine these by fits to independent data sets. We find that gas and haze opacity alone, with the temperatures fixed by Voyager observations, produces a model that is within a few percent of radiative convective balance everywhere in the atmosphere. In a self-consistent computation of temperatures, we find that our model calculation for the surface temperature is, in general, colder than the observed value by 5-10 degrees K. The presence or absence of methane condensation clouds only slightly alters the results. Good agreement can be obtained by adjusting the parameters in the model. The model parameters in these optimized cases are typically within 15% of the baseline values and within the limits allowed by observations. We conclude that the most important factors controlling Titan's thermal structure are absorption of sunlight by the stratospheric haze and the pressure-induced gas opacity in the infrared. Within the uncertainties of the model, these effects can explain the observed temperature profile. Condensation clouds play a minor role, if any.
Infrared spectra of Io in the region 2.5-5.0 micrometers, including new observational data, are analyzed using detailed laboratory studies of plausible surface ices. Besides the absorption bands attributable to sulfur dioxide frosts, four infrared spectral features of Io are shown to be unidentified. These unidentified features show spatial and temporal band strength variations. One pair is centered around 3.9 micrometers (3.85 and 3.91 micrometers) and the second pair is centered around 3.0 micrometers (2.97 and 3.15 micrometers). These absorptions fall close to the fundamental stretching modes in H2S and H2O, respectively. The infrared absorption spectra of an extensive set of laboratory ices ranging from pure materials, to binary mixtures of H2S and H2O (either mixed at different concentrations or layered), to H2O:H2S:SO2 mixtures are discussed. The effects of ultraviolet irradiation (120 and 160 nm) and temperature variation (from 9 to 130 K) on the infrared spectra of the ices are examined. This comparative study of Io reflectance spectra with the laboratory mixed ice transmission data shows the following: (1) Io's surface most likely contains H2S and H2O mixed with SO2. The 3.85- and 3.91-micrometers bands in the Io spectra can be accounted for by the absorption of the S-H stretching vibration (nu 1) in H2S clusters and isolated molecules in an SO2-dominated ice. The weak 2.97- and 3.15-micrometers bands which vary spatially and temporally in the Io spectra coincide with the nu 3 and nu 1 O-H stretching vibrations of clusters of H2O molecules complexed, through hydrogen bonding and charge transfer interactions, with SO2. (2) The observations are well matched qualitatively by the transmission spectra of SO2 ices containing about 3% H2S and 0.1% H2O which have been formed by the condensation of a mixture of the gases onto a 100 K surface. (3) No new features are produced in the region 2.5 to 5.0 micrometers in the spectrum of these ices under prolonged ultraviolet irradiation or temperature variation up to 120 K. (4) Comparison of the Io spectra to transmission spectra of both mixed molecular ices and layered ices indicates that only the former can explain the shifts and splitting of the absorption bands seen in the Io spectrum and additionally can account for the fact that solid H2S is observed in the surface material of Io at temperature and pressure conditions above the sublimation point of pure H2S.
Mass fractionation by hydrodynamic hydrogen escape is a promising mechanism for explaining the observed elemental and isotopic abundance patterns in terrestrial planet atmospheres. Previous work has considered only pure hydrogen winds. Here, the theory of mass fractionation by hydrogen escape is extended to atmospheres in which hydrogen is not the only major constituent. Analytical solutions are derived for cases in which all relevant atmospheric constituents escape; both analytical and numerical solutions are obtained for cases in which important heavy constituents are retained. In either case the fractionation patterns that result can differ significantly from those produced by pure hydrogen winds. Three applications of the theory are discussed: (1) The observed fractionation of terrestrial atmospheric neon with respect to mantle neon can be explained as a by-product of diffusion-limited hydrogen escape from a steam atmosphere toward the end of accretion. (2) The anomalously high Martian (SNC) 38Ar/36Ar ratio is attributed to hydrodynamic fractionation by a vigorously escaping, nearly pure hydrogen wind. (3) It is possible that the present high Martian D/H ratio was established during the same hydrodynamic escape phase that fractionated argon, but the predicted degree of D/H enrichment is sensitive to other, less well constrained parameters.
In this paper, we show that a wide variety of common soil bacteria are able to obtain their carbon and energy needs from tholin (a class of complex organic heteropolymers thought to be widely distributed through the solar system; in this case tholin was produced by passage of electrical discharge through a mixture of methane, ammonia, and water vapor). We have isolated aerobic, anaerobic, and facultatively anaerobic bacteria which are able to use tholin as a sole carbon source. Organisms which metabolize tholin represent a variety of bacterial genera including Clostridium, Pseudomonas, Bacillus, Acinetobacter, Paracoccus, Alcaligenes, Micrococcus, Corynebacterium, Aerobacter, Arthrobacter, Flavobacterium, and Actinomyces. Aerobic tholin-using bacteria were first isolated from soils containing unusual or sparse carbon sources. Some of these organisms were found to be facultatively anaerobic. Strictly anaerobic tholin-using bacteria were isolated from both carbon-rich and carbon-poor anaerobic lake muds. In addition, both aerobic and anaerobic tholin-using bacteria were isolated from common soil collected outside the laboratory building. Some, but not all, of the strains that were able to obtain carbon from tholin were also able to obtain their nitrogen requirements from tholin. Bacteria isolated from common soils were tested for their ability to obtain carbon from the water-soluble fraction, the ethanol-soluble fraction, and the water/ethanol-insoluble fraction of the tholin. Of the 3.5 x 10(7) bacteria isolated per gram of common soils, 1.7, 0.5, and 0.2%, respectively, were able to obtain their carbon requirements from the water-soluble fraction, the ethanol-soluble fraction and the water/ethanol-insoluble fraction of the tholin. The palatability of tholins to modern microbes may have implications for the early evolution of microbial life on Earth. Tholins may have formed the base of the food chain for an early heterotrophic biosphere before the evolution of autotrophy on the early Earth. Where tholins are present on other planets, they could possibly be metabolized by contaminant microorganisms transported to these bodies via spacecraft. Thus, the presence of tholins should be taken into account when evaluating the planetary quarantine requirements for probes to other planets.
Laboratory measurements of Steffes (1986) have suggested that the intensity and shape of the microwave spectrum of Venus might be especially sensitive to the subcloud abundance of constituents such as SO2 and gaseous H2SO4. It was likewise suggested that some variations of the shape of the emission spectrum might occur between 1.5 and 3 cm (10 to 20 GHz), a wavelength range which had previously only been sparsely observed. As a result, coordinated observations of Venus emission were conducted at four wavelengths between 1.35 cm (22.2 GHz) and 3.6 cm (8.42 GHz) using the 43-m NRAO antenna at Green Bank, West Virginia, and the 64-m antenna at NASA's Deep Space Communication Complex, Goldstone, California. In this paper, we report the methodology and results of these observations, and compare the results with other observations and with calculated emission spectra. We conclude that the observed emission spectrum is consistent with an average subcloud abundance of gaseous H2SO4 in equatorial and midlatitude regions which is approximately 5 ppm. It is suggested that additional measurements of atmospheric microwave opacity be made with the Pioneer-Venus Orbiter Radio Occultation experiment to search for temporal and spatial variations in gaseous H2SO4 abundance in the Venus atmosphere. An upper limit for the subcloud abundance of SO2 is also determined.
The prospect of life on Mars today is daunting. Especially problematic for a potential life form is a lack of water, particularly in a liquid state; extremely cold temperatures; ultraviolet and ionizing radiation; and soil oxidants. Yet, "oases" where life might persist have been suggested to occur in rocks (in analogy with endolithic microorganisms described from deserts around the world), in polar ice caps (in analogy with snow and ice algae) and in possible volcanic regions (in analogy with chemoautotrophs living in deep sea hydrothermal vents); all are critically examined. Microorganisms are known to be able to survive in salt crystals, and recently it has been shown that organisms can metabolize while encrusted in evaporites. Because evaporites are thought to occur on Mars and can attenuate light in the UV range while being far more transparent to radiation useful for photosynthesis (400-700 nm), and because of the properties of these "endoevaporitic" organisms, I propose that such communities provide a new model system for studying potential life on Mars. On the basis of this model, I suggest possibilities for site selection for future exobiological experiments on Mars.
We have estimated the D/H ratio that may have been present in the primitive ices in the protosolar nebula. Using observations of the CH3D/CH4 ratio in the outer planets, we developed two simple but limiting models which constrain the amount of dilution that deuterated volatiles which were contributed to the planetary atmospheres by evaporated primordial ices may have undergone by mixing with the original hydrogen envelopes. The models suggest that the D/H ratio in these ices was probably somewhere between a few times 10(-4) and 10(-3). These planetary-atmosphere-derived results are compared with other solar system bodies thought to contain primitive material and with D/H ratios observed in interstellar polyatomic molecules.
We report on new observations of Titan with the International Ultraviolet Explorer in the mid-UV range (lambda approximately 220-335 nm). We use these data to determine upper limits for the abundances of simple organic compounds in the gas phase and to further constrain the properties of the high altitude haze on Titan. As a baseline, we adopted the parametrized microphysical model of McKay et al. (1989) which is successful at reproducing Titan's thermal structure while satisfying several other observational constraints in the visible and IR regions. However, we find that such a model--in which all particles at a given altitude are assumed to have the same size--cannot match simultaneously the IUE observations and the visible/IR data, even when allowance is made for a wide range of values in the adjustable parameters. On the other hand, a good overall agreement is obtained when considering a biomodal size distribution, with small haze particles or "polymers" (r < 0.02 micrometer) acting as strong Rayleigh absorbers below 300 nm and larger haze particles (r approximately 0.1-0.5 micrometer) being responsible for the characteristics of the albedo spectrum in the near-UV, visible, and IR regions. This approach is consistent with the results of several previous investigations of the properties of Titan's haze, although our preferred vertical structure for the haze + polymer material somewhat differs from earlier solutions. On the basis of simple dynamical considerations, we adopted a uniformly mixed layer between 150 and 600 km. The IUE data allow us to place fairly stringent constraints on the abundance of the Rayleigh absorbers, if we assume that their optical properties are similar to those of laboratory-synthesized "tholins": The column-mass density of this material--the essential observable that can be determined from our study--is of the order of 5 micrograms cm-2. This would correspond to number-densities between 10(3) and 10(7) cm-3 in the 150-600 km altitude range, if the average particle radius is between 0.001 and 0.02 micrometer. Such high number densities are a priori at odds with the estimated coagulation lifetime for particles of that size. Thus, our proposed bimodal size distribution is plausible only if inhibiting processes act to slow down considerably the coagulation of polymers in Titan's stratosphere.
We have employed a simple climate model of early Mars in order to estimate the duration of ice-covered lakes after the onset of freezing conditions on Mars. The critical parameter determining the existence of ice-covered lakes is the existence of peak seasonal temperatures above freezing. The peak temperature occurs at the subsolar point at perihelion. We use the weathering model of Pollack et al. (Icarus 71, 203-224, 1987) to compute the pressure and temperature evolution of the atmosphere. We have included the variability of the solar luminosity. We find that if there was a source of ice to provide meltwater, liquid water habitats could have been maintained under relatively thin ice covers for up to 700 million years after mean global temperatures fell below the freezing point. At this point, the mean annual temperature is 227 K, and the pressure of atmospheric CO2 is about 0.5 bar. Without the presence of stable bodies of liquid water, it is not clear what mechanisms were responsible for the removal of this remaining CO2. From a biological point of view, we find that the duration of liquid water habitats on early Mars exceeds the upper limit on the time required for the origin of life on Mars.