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: 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.

Description: Erosion of the Martian surface by the flow of liquid water has apparently taken place at different times and locations on the planet. Many attempts were made to explain the valley networks by invoking a strong atmospheric CO2/H2O greenhouse early in the history of the planet. It was assumed that the large amounts of CO2 necessary to cause the greenhouse would have disappeared due to carbonate formation. Carbonates have yet to be positively identified. Volcanism has occurred throughout much of the history of Mars. Presumably gases such as SO2 were released along with CO2 and H2O. Estimates of amounts and rates with which SO2 were released into the Martian atmosphere, and how this would effect the global climate were made. Studies are continuing on the effects of SO2 and other volcanic gases on Martian climatic history.

Description: The adsorption of both CO2 and H2O was measured, under conditions of temperature and partial pressure similar to Mars, for a variety of absorbents. Both adsorb at coverages that exceed a monolayer at their respective Martian abundances. Clearly, their simultaneous presence in the Martian atmosphere will result in coadsorption of both at concentrations that may differ greatly from those measured during separate measurements. To the best of our knowledge, no data exists on the coadsorption of both gases. Co-adsorption experiments were begun and pertinent results will be reported. In the meantime the predicted behavior of such a system was mathematically explored as a compliment to the data, and to aid in its eventual interpretation.

Description: Among the questions to be addressed by a Mars Sample Return Mission are the history of the Martian climate and the mechanisms that control the volatile cycles. Unfortunately, the evidence that bears most strongly on those issues lies in the volatile distribution in, and physical configuration of, a very delicate and volatile system: the uppermost Martian regolith. Some useful measurements to be made on returned samples of the regolith are identified, along with the many critical considerations in ensuring the usefulness of returned samples.

Description: Researchers reexamined radiative transfer models of early Mars that were advanced to show the existance of a greenhouse effect. These models were reexamined with regard to the effect that regolith adsorption may have had. It is argued that while the precipitation of carbonates has probably been an important process during Mars history, the rates at which this process could have taken place under early Mars conditions would have dropped sharply once liquid water was fairly scarce. Furthermore, conditions under which liquid water was available may have involved efficient recycling of carbonate so that steady state conditions rather than irreversible CO2 removal prevailed. In contrast, the growth of regolith surface area demands corresponding and predictable CO2 removal from the atmosphere-cap system and is fully capable of terminating any enhanced temperature regime on early Mars in the absence of any other effects.