ALBERT

Description: Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Description: Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

Description: A 1D numerical model of the exchange of H2O between the atmosphere and subsurface of Mars through the PBL is employed to explore the mechanisms of H2O exchange and to elucidate the role played by the regolith in the local H2O budget. The atmospheric model includes effects of Coriolis, pressure gradient, and frictional forces for momentum: radiation, sensible heat flux, and advection for heat. It is suggested that in most cases, the flux through the Martian surface reverses twice in the course of each sol. The effects of surface albedo, thermal inertia, solar declination, atmospheric optical depth, and regolith pore structure are explored. It is proposed that higher thermal inertia forces more H2O into the atmosphere because the regolith is warmer at depth.

Description: The paper examines evidence that the Martian climate undergoes quasi-periodic variations, including the polar layered terrain, differences between the residual polar caps, and the current net southward flow of H2O. The driving functions for these variations are oscillations in the elements of the Martian orbit coupled with precession of the Martian spin axis. These 'astronomic variations' control the distribution of the insolation, which in turn influences the partition of volatiles between atmospheric and surface reservoirs. The major effects anticipated at low obliquity are growth of the polar caps, substantial decrease in surface pressure, cessation of duststorms, release of CO2 from the regolith, and poleward migration of H2O ground ice. At high obliquity, the mass of the perennial polar caps decreases and permanent CO2 frost disappears, CO2 desorbs from the regolith at high latitudes, the surface pressure may increase to several times its current value, and the atmospheric dust load increases.

Description: Spectral data from earth observations have indicated the presence of N2 and CH4 on Triton. This paper outlines the use of the 1-D radiative-convective model developed for Titan to calculate the current pressure of N2 and CH4 on Triton. The production of haze material is obtained by scaling down from the Titan value. Results and predictions for the Voyager Triton encounter are as follows: A N2-CH4 atmosphere on Triton is thermodynamically self consistent and would have a surface pressure of approximately 50 millibar; due to the chemically produced haze, Triton has a hot atmosphere with a temperature of approximately 130 K; Triton's troposphere is a region of saturation of the major constituent of the atmosphere, N2.

Description: A goal of this research is to develop conceptual designs for instrumentation to perform in situ measurements of the Martian soil in order to determine the existence and nature of any reactive chemicals. Our approach involves assessment and critical review of the Viking biology results which indicated the presence of a soil oxidant, an investigation of the possible application of standard soil science techniques to the analysis of Martian soil, and a preliminary consideration of non-standard methods that may be necessary for use in the highly oxidizing Martian soil. Based on our preliminary analysis, we have developed strawman concepts for standard soil analysis on Mars, including pH, suitable for use on a Mars rover mission. In addition, we have devised a method for the determination of the possible strong oxidants on Mars.

Description: Both Viking landers found evidence of water in small concentration in the soils of Mars. Using the gas chromatograph mass spectrometer the soil samples on Mars were heated to 500 C to release the water. This result lead researchers to believe that the water in the soil of Mars was tightly bound in a hydration state. In the laboratory several Mars analog soils and a few bench mark soils were run through a microwave to determine the amount of water released using this method. The results suggest that sufficient water can be obtained using this method to augment the activities of a human base on Mars.

Description: For most estimates of available regolith and initial degassed CO(sub 2) inventories, it appears that any initial inventory must have been lost to space or incorporated into carbonates. Most estimates of the total available degassed CO(sub 2) inventory are only marginally sufficient to allow for a major early greenhouse effect. It is suggested that the requirements for greenhouse warming to produce old dessicated terrain would be greatly lessened if groundwater brines rather than rainfall were involved and if a higher internal gradient were involved to raise the water (brine) table, leading to more frequent sapping.

Description: Experimental data is presented for CO2 adsorption on palagonites (now thought to provide the most acceptable spectral match to Mars weathering products). When corrected for great differences in specific surface area, the adsorptive behavior exhibited by palogonites, nontronite, and basalt with respect to CO2 can be (approx.) described by the same generic equation. Using this relationship normalized to a Mars soil surface area, and the dependence of subsurface temperatures on latitude and depth, the current inventory of regolith absorbed CO2 was estimated.

Description: The current paradigm for quasi-periodic climate change on Mars holds that perhaps a few hundred millibars of CO2 are available for exchange between the atmosphere and regolith, and that a vast majority of that CO2 is presently absorbed into the regolith. The CO2 is partitioned between the regolith and atmosphere according to an equilibrium adsorptive relationship. If the atmospheric pressure exceeds the frost point at or near the poles, then quasi-permanent polar caps form and buffer the atmospheric pressure. This model was developed based upon laboratory studies of CO2 adsorption where no other adsorbates are present. We will conduct laboratory measurements of the simultaneous adsorption of H2O and CO2 under Mars-like conditions, and develop numerical expressions for use in climate modeling based upon our results.