Concentration modulation by thermal decomposition for multiplex gas chromatography.
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Alkadienes↗
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Mechanical modulation for multiplex gas chromatographic analyses at subatmospheric pressures.
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Alkanes↗
Development of a modulator to measure water vapor selectively in a gaseous mixture.
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Atmosphere↗
Preservation of biological information in thermal spring deposits: developing a strategy for the search for fossil life on Mars.
Current interpretations of the early history of Mars suggest many similarities with the early Earth and therefore raise the possibility that the Archean and Proterozoic history of life on Earth could have a counterpart on Mars. Terrestrial experience suggests that, with techniques that can be employed remotely, ancient springs, including thermal springs, could well yield important information. By delivering water and various dissolved species to the sunlit surface of Mars, springs very likely created an environment suitable for life, which could have been difficult, if not impossible, to attain elsewhere. The chemical and temperature gradients associated with thermal springs sort organisms into sharply delineated, distinctive and different communities, and so diverse organisms are concentrated into relatively small areas in a predictable and informative fashion. A wide range of metabolic strategies are concentrated into small areas, thus furnishing a useful and representative sampling of the existing biota. Mineral-charged springwaters frequently deposit chemical precipitates of silica and/or carbonate which incorporate microorganisms and preserve them as fossils. The juxtaposition of stream valley headwaters with volcanoes and impact craters on Mars strongly implies that subsurface heating of groundwater created thermal springs. On Earth, thermal springs create distinctive geomorphic features and chemical signatures which can be detected by remote sensing. Spring deposits can be quite different chemically from adjacent rocks. Individual springs can be hundreds of meters wide, and complexes of springs occupy areas up to several kilometers wide. Benthic microbial mats and the resultant stromatolites occupy a large fraction of the available area. The relatively high densities of fossils and microbial mat fabrics within these deposits make them highly prospective in any search for morphological evidence of life, and there are examples of microbial fossils in spring deposits as old as 300 Myr.
Bacteria↗
Coupled atmosphere-ocean models of Titan's past.
We have developed a coupled atmosphere and ocean model of Titan's surface. The atmospheric model is a 1-D spectrally-resolved radiative-convective model. The ocean thermodynamics are based upon solution theory. The ocean, initially composed of CH4, becomes progressively enriched in ethane over time. The partial pressures of N2 and CH4 in the atmosphere are dependent on the ocean temperature and composition. We find that the resulting system is stable against a runaway greenhouse. Accounting for the decreased solar luminosity, we find that Titan's surface temperature was about 20 K colder 4 Gyr ago. Without an ocean, but only small CH4 lakes, the temperature change is 12 K. In both cases we find that the surface of Titan may have been ice covered about 3 Gyr ago. In the lakes case condensation of N2 provides the ice, whereas in the ocean case the ocean freezes. The dominant factor influencing the evolution of Titan's surface temperature is the change in the solar constant--amplified, if an ocean is present, by the temperature dependence of the solubility of N2. Accretional heating can dramatically alter the surface temperature; a surface thermal flux of 500 erg cm-2 sec-1, representative of small levels of accretional heating, results in a approximately 20 K change in surface temperatures.
Astronomical Phenomena↗
An experimental study of the organic molecules produced in cometary and interstellar ice analogs by thermal formaldehyde reactions.
Thermally promoted formaldehyde (H2CO) reactions in very low temperature ices have been studied to test their importance as a source of organic molecules in astrophysical environments such as comets and interstellar ices. The infrared absorption strengths of a number of the H2CO bands were measured in 10 K ices of pure H2CO and H20:H2CO = 100:3. Infrared spectroscopy was used to monitor the formaldehyde chemistry during warm-up of ices containing H2CO and one or more of the molecules H2O, CH3OH, CO, CO2, O2, and NH3. Formaldehyde reactions do not proceed at low temperatures in the absence of NH3. However, even small traces of NH3 (NH3/H2CO > or = 0.005) are sufficient to induce conversion of a considerable fraction (> 40%) of the H2CO into organic residues. Formaldehyde reactions were observed to start at temperatures as low as 40 K for NH3:H2CO binary ices and at approximately 80 K in astrophysically relevant (i.e., H2O-dominated) ices. A total of five different organic products of these reactions can be distinguished by infrared spectroscopy. One of them is polyoxymethylene (POM), a well-known H2CO polymerization product, whereas the others are reaction products of H2CO with H20, CH3OH and NH3. These all seem to be derivatives of polyoxymethylene. The nature of the components and their relative abundances depend strongly on the initial composition of the ice mixture as well as on the ice's irradiation history. We estimate that about 1% of the organics found in the coma of Comet Halley could have been produced by thermal formaldehyde reactions taking place in the nucleus.
Ammonia↗
The condensation and vaporization behavior of ices containing SO2, H2S, and CO2: implications for Io.
In an extension of previously reported work on ices containing CO, CO2, H2O, CH3OH, NH3, and H2, measurements of the physical and infrared spectral properties of ices containing molecules relevant to Jupiter's moon Io are presented. These include studies on ice systems containing SO2, H2S, and CO2. The condensation and sublimation behaviors of each ice system and surface binding energies of their components are discussed. The surface binding energies can be used to calculate the residence times of the molecules on a surface as a function of temperature and thus represent important parameters for any calculation that attempts to model the transport of these molecules on Io's surface. The derived values indicate that SO2 frosts on Io are likely to anneal rapidly, resulting in less fluffy, "glassy" ices and that H2S can be trapped in the SO2 ices of Io during night-time hours provided that SO2 deposition rates are on the order of 5 micrometers/hr or larger.
Carbon Dioxide↗
A coupled soil-atmosphere model of H2O2 on Mars.
The Viking Gas Chromatograph Mass Spectrometer failed to detect organic compounds on Mars, and both the Viking Labeled Release and the Viking Gas Exchange experiments indicated a reactive soil surface. These results have led to the widespread belief that there are oxidants in the martian soil. Since H2O2 is produced by photochemical processes in the atmosphere of Mars, and has been shown in the laboratory to reproduce closely the Viking LR results, it is a likely candidate for a martian soil oxidant. Here, we report on the results of a coupled soil/atmosphere transport model for H2O2 on Mars. Upon diffusing into the soil, its concentration is determined by the extent to which it is adsorbed and by the rate at which it is catalytically destroyed. An analytical model for calculating the distribution of H2O2 in the martian atmosphere and soil is developed. The concentration of H2O2 in the soil is shown to go to zero at a finite depth, a consequence of the nonlinear soil diffusion equation. The model is parameterized in terms of an unknown quantity, the lifetime of H2O2 against heterogeneous catalytic destruction in the soil. Calculated concentrations are compared with a H2O2 concentration of 30 nmoles/cm3, inferred from the Viking Labeled Release experiment. A significant result of this model is that for a wide range of H2O2 lifetimes (up to 10(5) years), the extinction depth was found to be less than 3 m. The maximum possible concentration in the top 4 cm is calculated to be approximately 240 nmoles/cm3, achieved with lifetimes of greater than 1000 years. Concentrations higher than 30 nmoles/cm3 require lifetimes of greater than 4.3 terrestrial years. For a wide range of H2O2 lifetimes, it was found that the atmospheric concentration is only weakly coupled with soil loss processes. Losses to the soil become significant only when lifetimes are less than a few hours. If there are depths below which H2O2 is not transported, it is plausible that organic compounds, protected from an oxidizing environment, may still exist. They would have been deposited by meteors, or be the organic remains of past life.
Atmosphere↗
Magnetically enhanced coagulation of very small iron grains.
Laboratory experiments, in which very small (approximately 20 nm) grains are produced in the presence of a magnetic field on the order of 100 Gauss in a low-pressure hydrogen atmosphere, have demonstrated that such smokes can become permanently magnetized. We show that magnetization results in an enormous enhancement in the coagulation efficiency of such materials even in the absence of external magnetic fields. Small iron grains should have been produced in the solar nebula by thermal processing of preexisting interstellar grains. If such processing occurred via high-energy electromagnetic events then the resultant magnetized grains could have triggered the formation of centimeter- to meter-sized protoplanetessimals by acting as "nets" capable of sweeping up nonconductive silicates suspended in the gas. It is possible that the presence of conductive fractal aggregates observed in modern-day protostellar disks could be explained by the enhanced coagulation efficiency of very small magnetized iron particles.
Astronomical Phenomena↗
Is H2O present on Io? The detection of a new strong band near 3590 cm-1 (2.79 micrometers).
A strong absorption band at 3590 +/- 20 cm-1 (2.790 +/- 0.015 micrometers) has been discovered in the spectrum of Io using the Kuiper Airborne Observatory (KAO). The 2 nu1 + nu3 combination mode of solid SO2 falls at this position. Since SO2 is abundant on Io it must contribute to the new band. However, a band due to H2O was predicted near this frequency in Io's spectrum based on laboratory experiments of H2O:SO2 mixed Io ice analogs which were used to assign the two weak, variable features of 3370 and 3170 cm-1 (2.97 and 3.15 micrometers) to trace amounts of H2O frozen in solid SO2 on Io. The new band probably originates from both SO2 and H2O. Unfortunately, the spectral resolution of the data is insufficient to settle the issue of whether there are two resolvable components.
Aircraft↗
H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere.
A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, phi H2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi H2SO4 = 2.2 x 10(12) cm-2 sec-1. The sulfur to sulfuric acid mass flux ratio in the clouds is 1 : 27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3 km-1 in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(12) cm-2 sec-1 in this model. Our second model, which is constrained to yield fH2SO4 = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O(30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; phi H2SO4 = 6.4 x 10(12) cm-2 sec-1; and phi co = 4.2 x 10(12) cm-2 sec-1. The S/H2SO4 flux mass ratio is 1 : 18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km-1 in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of formation of the lower cloud layer. Variations of the lower cloud layer are discussed. Our modeling of the OCS and CO profiles in the lower atmosphere measured by Pollack et al. (1993) provides a reasonable explanation of these data and shows that the rate coefficient of the reaction SO3 + CO --> CO2 + SO2 is equal to 10(-11) exp(-(13,100 +/- 1000)/T) cm3/s. The main channel of the reaction between SO3 and OCS is CO2 + (SO)2, and its rate coefficient is equal to 10(-11) exp(-(8900 +/- 500)T)cm3/s. In the conditions of Venus' lower atmosphere, (SO)2 is removed by the reaction (SO)2 + OCS --> CO + S2 + SO2. The model predicts an OCS mixing ratio of 28 ppm near the surface.
Atmosphere↗
A model for the evolution of CO2 on Mars.
We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model (1973, J. Atmos. Sci. 30, 1502-1508). The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and solar equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures>250 K) and wet (surface pressures>30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, <300 mbar in the regolith, and <5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (>1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not form initially, but can form later on, when weathering and escape lower the surface pressure to a point at which polar heating is no longer sufficient to prevent cap formation and the collapse of the climate system. Our modeling suggests this critical initial amount of CO2 is between 1 and 2 bar, but its true value will depend on all factors affecting the polar heat budget.
Atmosphere↗
Photochemical modeling of Titan's atmosphere
We have developed a new photochemical model of Titan's atmosphere which includes all the important compounds and reactions in spherical geometry from the surface to 1240 km. Compared to the previous model of Yung et al. (1984, Astrophys. J. Suppl. 55, 465-506), the most significant recent change in the reactions used is the updated methane photodissociation scheme (Mordaunt et al. 1993, J. Chem. Phys. 98(3), 2054-2065). Moreover, the transfer of the solar radiation in the atmosphere and the photolysis rates have been calculated by using a Monte Carlo code. Finally, the eddy diffusion coefficient profile is adjusted in order to fit the mean vertical distribution of HCN retrieved from millimeter groundbased observations of Tanguy et al. (1990, Icarus, 85, 43-57) using new values for the boundary flux of atomic nitrogen (Strobel et al. 1992, Icarus 100, 512-526). We have run the model in both steady-state and diurnal modes, with 62 speices involved in 249 reactions. There is little difference between diurnal and steady-state results. Overall our results are in a closer agreement with the abundances inferred from the Voyager infrared measurements at the equator than the Yung et al. results. We find that the catalytic scheme for H recombination invoked by Yung et al. only slightly improves the model results and we conclude that this scheme is not essential to fit observations.
Atmosphere↗
Titan's stratospheric temperature asymmetry: a radiative origin?
During the 1981 Voyager encounter, Titan's stratosphere exhibited a large thermal asymmetry, with high northern latitudes being colder than comparable southern latitudes. Given the short radiative time constant, this asymmetry would not be expected at the season of the Voyager observations (spring equinox), if the infrared and solar opacity sources were distributed symmetrically. We have investigated the radiative budget of Titan's stratosphere, using two selections of Voyager IRIS spectra recorded at symmetric northern and southern latitudes. In the region 0.1-1 mbar, temperatures are 7 K colder at 50 degrees N than at 53 degrees S and the difference reaches approximately 13 K at 5 mbar. On the other hand, the northern region is strongly enriched in nitriles and hydrocarbons, and the haze optical depth derived from the continuum emission between 8 and 15 micrometers is twice as large as in the south. Cooling rate profiles have been computed at the two locations, using the gas and haze abundances derived from the IRIS measurements. We find that, despite lower temperatures, the cooling rate profiles in the pressure range 0.15-5 mbar are 20 to 40% larger in the north than in the south, because of the enhanced concentrations of infrared radiators. Because the northern hemisphere appears darker than the southern one in the Voyager images, enhanced solar heating is also expected to take place at 50 degrees N. Solar heating rate profiles have been calculated, with two different assumptions on the origin of the hemispheric asymmetry. In the most likely case where it results from a variation in the absorbance of the haze material, the heating rates are found to be 12-15% larger at the northern location than at the southern one, a smaller increase than that in the cooling rates. If the lower albedo in the north results from an increase in the particle number density, a 55 to 75% difference is found for the pressure range 0.15-5 mbar, thus larger than that calculated for the cooling rates. Considering the uncertainties in the haze model, dynamical heat transport may significantly contribute to the meridional temperature gradients observed in the stratosphere. On the other hand, the latitudinal variation in gas and haze composition may be sufficient to explain the entire temperature asymmetry observed, without invoking a lag in the thermal response of the atmosphere due to dynamical inertia.
Atmosphere↗
Reflectance spectroscopy of ferric sulfate-bearing montmorillonites as Mars soil analog materials.
Spectroscopic analyses have shown that smectites enhanced in the laboratory with additional ferric species exhibit important similarities to those of the soils on Mars. Ferrihydrite in these chemically treated smectites has features in the visible to near-infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. New samples have been prepared with sulfate as well, because S was found by Viking to be a major component in the surface material on Mars. A suite of ferrihydrite-bearing and ferric sulfate-bearing montmorillonites, prepared with variable Fe3+ and S concentrations and variable pH conditions, has been analyzed using reflectance spectroscopy in the visible and infrared regions, Mössbauer spectroscopy at room temperature and 4 K, differential thermal analysis, and X-ray diffraction. These analyses support the formation of ferrihydrite of variable crystallinity in the ferrihydrite-bearing montmorillonites and a combination of schwertmannite and ferrihydrite in the ferric sulfate-bearing montmorillonites. Small quantities of poorly crystalline or nanophase forms of other ferric materials may also be present in these samples. The chemical formation conditions of the ferrihydrite-bearing and ferric sulfate-bearing montmorillonites influence the character of the low temperature Mössbauer sextets and the visible reflectance spectra. An absorption minimum is observed at 0.88-0.89 micrometers in spectra of the ferric sulfate-bearing samples, and at 0.89-0.92 micrometers in spectra of the ferrihydrate-bearing montmorillonites. Mössbauer spectra of the ferric sulfate-bearing montmorillonites indicate variable concentrations of ferrihydrite and schwertmannite in the interlaminar spaces and along grain surfaces. Dehydration under reduced atmospheric pressure conditions induces a greater effect on the adsorbed and interlayer water in ferrihydrite-bearing montmorillonite than on the water in ferric sulfate-bearing montmorillonite. Reflectance spectra of ferric sulfate-bearing montmorillonite include a strong 3-micrometers band that is more resistant to dry atmospheric conditions than the 3-micrometers band in spectra of similarly prepared ferrihydrite-bearing montmorillonites.
Aluminum Silicates↗
Numerical simulation of the general circulation of the atmosphere of Titan.
The atmospheric circulation of Titan is investigated with a general circulation model. The representation of the large-scale dynamics is based on a grid point model developed and used at Laboratoire de Météorologie Dynamique for climate studies. The code also includes an accurate representation of radiative heating and cooling by molecular gases and haze as well as a parametrization of the vertical turbulent mixing of momentum and potential temperature. Long-term simulations of the atmospheric circulation are presented. Starting from a state of rest, the model spontaneously produces a strong superrotation with prograde equatorial winds (i.e., in the same sense as the assumed rotation of the solid body) increasing from the surface to reach 100 m sec-1 near the 1-mbar pressure level. Those equatorial winds are in very good agreement with some indirect observations, especially those of the 1989 occultation of Star 28-Sgr by Titan. On the other hand, the model simulates latitudinal temperature contrasts in the stratosphere that are significantly weaker than those observed by Voyager 1 which, we suggest, may be partly due to the nonrepresentation of the spatial and temporal variations of the abundances of molecular species and haze. We present diagnostics of the simulated atmospheric circulation underlying the importance of the seasonal cycle and a tentative explanation for the creation and maintenance of the atmospheric superrotation based on a careful angular momentum budget.
Atmosphere↗
Simulations of Titan's brightness by a two-dimensional haze model.
We have used a 2-D microphysics model to study the effects of atmospheric motions on the albedo of Titan's thick haze layer. We compare our results to the observed variations of Titan's brightness with season and latitude. We use two wind fields; the first is a simple pole-to-pole Hadley cell that reverses twice a year. The second is based on the results of a preliminary Titan GCM. Seasonally varying wind fields, with horizontal velocities of about 1 cm sec-1 at optical depth unity, are capable of producing the observed change in geometric albedo of about 10% over the Titan year. Neither of the two wind fields can adequately reproduce the latitudinal distribution of reflectivity seen by Voyager. At visible wavelengths, where only haze opacity is important, upwelling produces darkening by increasing the particle size at optical depth unity. This is due to the suspension of larger particles as well as the lateral removal of smaller particles from the top of the atmosphere. At UV wavelengths and at 0.89 micrometers the albedo is determined by the competing effects of the gas the haze material. Gas is bright in the UV and dark at 0.89 micrometers. Haze transport at high altitudes controls the UV albedo and transport at low altitude controls the 0.89 micrometers albedo. Comparisons between the hemispheric contrast at UV, visible, and IR wavelengths can be diagnostic of the vertical structure of the wind field on Titan.
Atmosphere↗
A matched filter method for ground-based sub-noise detection of terrestrial extrasolar planets in eclipsing binaries: application to CM Draconis.
The photometric detection of extrasolar planets by transits in eclipsing binary systems can be significantly improved by cross-correlating the observational light curves with synthetic models of possible planetary transit features, essentially a matched filter approach. We demonstrate the utility and application of this transit detection algorithm for ground-based detections of terrestrial-sized (Earth-to-Neptune radii) extrasolar planets in the dwarf M-star eclipsing binary system CM Draconis. Preliminary photometric observational data of this system demonstrate that the observational noise is well characterized as white and Gaussian at the observational time steps required for precision photometric measurements. Depending on planet formation scenarios, terrestrial-sized planets may form quite close to this low-luminosity system. We demonstrate, for example, that planets as small as 1.4 Earth radii with periods on the order of a few months in the CM Draconis system could be detected at the 99.9% confidence level in less than a year using 1-m class telescopes from the ground. This result contradicts commonly held assumptions limiting present ground-based efforts to, at best, detections of gas giant planets after several years of observation. This method can be readily extended to a number of other larger star systems with the utilization of larger telescopes and longer observing times. Its extension to spacecraft observations should also allow the determination of the presence of terrestrial-sized planets in nearly 100 other known eclipsing binary systems.
Algorithms↗