Simulations of the Viking Gas Exchange Experiment using palagonite and Fe-rich montmorillonite as terrestrial analogs: implications for the surface composition of Mars.

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.

Derivation of midinfrared (5-25 micrometers) optical constants of some silicates and palagonite.

The midinfrared 2000-400 cm-1 (5-25 micrometers) optical constants (real (n) and imaginary (k) indices of refraction) are presented for: (1) pyrophyllite; (2) kaolinite; (3) serpentine; (4) montmorillonite; (5) saponite; (6) palagonite; and (7) orthopyroxene. Comparison of the values derived here with those previously presented for serpentine, montmorillonite, and palagonite is generally quite good and discrepancies between values are probably due to either chemical differences between the actual samples or different techniques used to derive the values. For montmorillonite, saponite, and palagonite we were able to derive optical constants in the region of the H2O-bending fundamental near 6 micrometers. We find that if a pellet of pure material can be produced with a mirror-like surface then the optical constants of clays and other noncohesive materials can be readily derived.

The biogeochemical cycle of the adsorbed template. II: Selective adsorption of mononucleotides on adsorbed polynucleotide templates.

Experimental results are presented for the verification of the specific interaction step of the 'adsorbed template' biogeochemical cycle, a simple model for a primitive prebiotic replication system. The experimental system consisted of gypsum as the mineral to which an oligonucleotide template attaches (Poly-C or Poly-U) and 5'-AMP, 5'-GMP, 5'-CMP and 5'-UMP as the interacting biomonomers. When Poly-C or Poly-U were used as adsorbed templates, 5'-GMP and 5'-AMP, respectively were observed to be the most strongly adsorbed species. Moreover, there exists a direct quantitative relationship between the quantity of cytidine or uracil residues in the adsorbed state and the amount of the complementary mononucleotide that is attached to it. NaCl added to the system in order to create conditions of high ionic strength seems to enhance the selectivity of the adsorption of the monmucleotides to these adsorbed templates.

Laboratory investigations of Mars: chemical and spectroscopic characteristics of a suite of clays as Mars soil analogs.

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.

Comparison of automated pre-column and post-column analysis of amino acid oligomers.

It has been shown that various amino acids will polymerize under plausible prebiotic conditions on mineral surfaces, such as clays and soluble salts, to form varying amounts of oligomers (n = 2-6). The investigations of these surface reactions required a quantitative method for the separation and detection of these amino acid oligomers at the picomole level in the presence of nanomole levels of the parent amino acid. In initial high-performance liquid chromatography (HPLC) studies using a classical postcolumn o-phthalaldehyde (OPA) derivatization ion-exchange HPLC procedure with fluorescence detection, problems encountered included lengthy analysis time, inadequate separation and large relative differences in sensitivity for the separated species, expressed as a variable fluorescent yield, which contributed to poor quantitation. We have compared a simple, automated, pre-column OPA derivatization and reversed-phase HPLC method with the classical post-column OPA derivatization and ion-exchange HPLC procedure. A comparison of UV and fluorescent detection of the amino acid oligomers is also presented. The conclusion reached is that the pre-column OPA derivatization, reversed-phase HPLC and UV detection produces enhanced separation, improved sensitivity and faster analysis than post-column OPA derivatization, ion-exchange HPLC and fluorescence detection.

Soluble minerals in chemical evolution. II. Characterization of the adsorption of 5'-AMP and 5'-CMP on a variety of soluble mineral salts.

The adsorption of 5'-AMP and 5'-CMP was studied in saturated solutions of several soluble mineral salts (NaCl, Na2SO4, MgCl2 X 6H2O, MgSO4 X 7H2O, CaCl2 X 2H2O, CaSO4 X 2H2O, SrCl2 X 6H2O, SrSO4, and ZnSO4 X 7H2O) as a function of pH, ionic strength, and surface area of the solid salt. The adsorption shows a pH dependence; this can be correlated with the charge on the nucleotide molecule which is determined by the state of protonation of the N-1 nitrogen of 5'-AMP or N-3 nitrogen of 5'-CMP and the phosphate oxygens. The adsorption which results from the binding between the nucleotide molecule and the salt surface is proposed as being due to electrostatic forces. It was concluded that the adsorption was reversible in nature. The adsorption shows a strong dependence upon ionic strength and decreases with increasing ionic strength. Surface area is shown to be an important factor in evaluating and comparing the magnitude of adsorption of nucleotides onto various mineral salts. The implications of the results of the study are discussed in terms of the importance of soluble mineral salts as adsorption sites in the characterization of the adsorption reactions of an adsorbed template in biogeochemical cycles.

The biogeochemical cycle of the adsorbed template. I: Formation of the template.

Experimental results are presented for the verification of the first adsorption step of the 'adsorbed template' biogeochemical cycle, a simple model for a primitive prebiotic replication system. The adsorption of Poly-C, Poly-U, Poly-A, Poly-G, and 5'-AMP, 5'-GMP, 5'-CMP and 5'-UMP onto gypsum was studied. It was found that under the conditions of the experiment, the polymers have a very high affinity for the mineral surface, while the monomers adsorb much less efficiently.

Soluble minerals in chemical evolution. I. Adsorption of 5'-AMP on CaSO4--a model system.

The adsorption of 5'-AMP onto solid CaSO4 2H2O was studied in a saturated suspension as a function of pH and electrolyte concentration. The adsorption is pH-dependent and is directly correlated with the charge on the 5'-AMP molecule which is determined by the state of protonation of the N-1 nitrogen of the purine ring and the phosphate oxygens. It is proposed that the binding occurs between the nucleotide and the salt is electrostatic in nature. The adsorption decreases with increasing ionic strength of the solution which means that in a fluctuating environment of wetting and drying cycles, a biomolecule similar to 5'-AMP could be expected to desorb during the drying phase. The results indicate that CaSO4 2H2O can serve as a concentrating surface for biomolecules. The significance of this is discussed with regard to the possible role of soluble minerals and their surfaces in a geochemical model consistent with the evolution of the Earth and the origin of life.

pH profile of the adsorption of nucleotides onto montmorillonite. I. Selected homoionic clays.

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.

pH profile of the adsorption of nucleotides onto montmorillonite. II. Adsorption and desorption of 5'-AMP in iron-calcium montmorillonite systems.

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.

Binding of nickel (II) to 5'-nucleoside monophosphates and related compounds.

The interactions of Ni(II) cation with a representative suite of purine bases and the respective nucleosides and nucleotides have been studied by ultraviolet difference spectroscopy. Apparent association constants, Kapp, were determined for each system at pH 7.0, using computer linear regression coupled with an iteration technique. The specificity of binding of Ni2+ for the purine nucleotides studied at pH 7.0 was 5'-GMP greater than 5'-IMP greater than 5'-AMP; a similar ordering was also found for the respective nucleosides and bases. In this study binding was not observed for the suite of pyramidines used, although a Ni2+ - cytidine complex has been observed (Fiskin and Beer, 1965). It was also found that Ni2+ bound more strongly to the purine 5'-nucleotides than to the respective nucleosides and bases. These trends are explained in terms of metal-ligand bonds and available bonding positions on the ligands. A role for metal-ion-nucleotide types of complexes is suggested in the processes that might have given rise to the origin of life.

Logarithmic converter for atomic-absorption spectrometry.

A logarithmic converter using a silicon transistor in the feed-back loop of an operational amplifier circuit, and suitable for use with a double-beam atomic-absorption spectrometer, is described.