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Simulations of the Gas Exchange Experiment (GEX), one of the Viking Lander Biology Experiments, were run using palagonite and Fe-rich montmorillonite as terrestrial analogs of the Martian soil. These terrestrial analogs were exposed to a nutrient solution of the same composition as that of the Viking Landers under humid (no contact with nutrient) and wet (intimate contact) conditions. The headspace gases in the GEX sample cell were sampled and then analyzed by gas chromatography under both humid and wet conditions. Five gases were monitored: CO2, N2, O2, Ar, and Kr. It was determined that in order to simulate the CO2 gas changes of the Viking GEX experiment, the mixture of soil analog mineral plus nutrient medium must be slightly (pH = 7.4) to moderately basic (pH = 8.7). This conclusion suggests constraints upon the composition of terrestrial analogs to the Mars soil; acidic components may be present, but the overall mixture must be basic in order to simulate the Viking GEX results.

The effect of adsorbed ions and pH on the adsorption of several purine and pyrimidine nucleotides on montmorillonite was studied. The cations used to prepare homoionic montmorillonite was Na+, Mn2+, Fe3+, Co2+, Ni+, Cu2+, and Zn2+. The nucleotides studied were 5'-,3'-, and 2'-AMP, and 5'-CMP in the pH range 2 through 12. The results show that preferential adsorption amongst nucleotides and similar molecules is dependent upon pH and the nature of the substituted metal cation in the clay. At neutral pH, it was observed that 5'-AMP was more strongly adsorbed than 2'AMP, 3'-AMP, and 5'-CMP. Cu2+ and Zn2+ clays showed enhanced adsorption of 5'-AMP compared to the other cation clays studied in the pH range 4-8. Below pH 4, the adsorption is attributed to cation and anion exchange adsorption mechanisms: above pH 4, anion exchange may also occur, but the adsorption (when it occurs) likely depends on a complexation mechanism occurring between metal cation in the clay exchange site the biomolecule. It is thus proposed that homoionic clays may have played a significant role in the concentration mechanism of biomonomers in the prebiotic environment, a prerequisite step necessary for the formation of biopolymers in the remaining steps leading to the origin of life.

The interaction of 5'-AMP with montmorillonite saturated with various ratios of two metals found ubiquitously on the surface of Earth, that is, iron and calcium, is investigated. Adsorption and desorption of the nucleotide were studied in the pH range of 2-12 at three levels of addition: 0.080, 0.268 and 0.803 mmole 5'-AMP per gram of clay. Two desorption stages were employed--H2O wash and NaOH extraction (pH = 12.0). 5'-AMP was preferentially adsorbed on the Fe-containing clays relative to the Ca clay. The nucleotide was fully recovered by the two desorption stages, mostly by the NaOH extraction. The evidence at hand indicates that 5'-AMP reaction with clay is affected by electrostatic interactions involving both attraction and repulsion forces. Some specific adsorption, possibly the result of covalent bonding and complex formation with the adsorbed ion, cannot be ruled out for iron but does not appear to operate for calcium. Changes in pH cause varying degrees of attraction and repulsion of 5'-AMP and may have been operating on the primitive Earth, leading to sequences of adsorption and release of this biomolecule.

Two major questions have been raised by prior explorations of Mars. Has there ever been abundant water on Mars? Why is the iron found in the Martian soil not readily seen in the reflectance spectra of the surface? The work reported here describes a model soil system of Mars Soil Analog Materials, MarSAM, with attributes which could help resolve both of these dilemmas. The first set of MarSAM consisted of a suite of variably iron/calcium-exchanged montmorillonite clays. Several properties, including chemical composition, surface-ion composition, water adsorption isotherms, and reflectance spectra, of these clays have been examined. Also, simulations of the Viking Labeled Release Experiment using the MarSAM were performed. The results of these studies show that surface iron and adsorbed water are important determinants of clay behavior as evidenced by changes in reflectance, water absorption, and clay surface reactions. Thus, these materials provide a model soil system which reasonably satisfies the constraints imposed by the Viking analyses and remote spectral observations of the Martian surface, and which offers a sink for significant amounts of water. Finally, our initial results may provide insights into the mechanisms of reactions that occur on clay surfaces as well as a more specific approach to determining the mineralogy of Martian soils.