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A feasibility study assessing the utility of the adaptation of near infrared correlation spectroscopy to quantifying iron and adsorbed water in some clay-based Mars soil analog materials (MarSAM's). The work was intended to constitute Phase 1 of an approach to identifying optical analytical wavelength regions, not only for important mineral classes, but for chemically active centers within them. Many of these centers are common to unrelated mineral classes and of disproportionate influence relative to the mineral structure as a whole in determining the surface reactivity of mineral surfaces. We previously reported linearity between reflectance and total iron and total moisture over a large range of both key variables. We also discovered interesting relationships between the intensity of iron bands and the relative humidity of the systems. These relationships were confirmed. We also show that, in the low humidity range, reflectance is linearly dependent on a different kind of water from that best representing the full humidity range (the kind of water associated, in clays, with surface acidity). These relationships and the sensitivity and capability of quantitation of near infrared data indicate high promise with the production of reactive surface intermediates of products of surface reactions.

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Martian surface morphology suggests the presence of liquid H2O on Mars in the past. Reflectance spectra of the Martian surface include features which correspond to the crystal field transitions of iron, as well as features supporting the presence of ice and minerals containing structural OH and surface water. Researchers initiated further spectroscopic studies of surface iron and water and structural OH in clays in order to determine what remotely obtained spectra can indicate about the presence of clays on Mars based on a clearer understanding of the factors influencing the spectral features. Current technology allows researchers to better correlate the low frequency fundamental stretching and bending vibrations of O-H bonds with the diagnostic near infrared overtone and combination bands used in mineral characterization and identification.

The rates (previously reported) for the air oxidation of hydrazine on kaolinite and substituent oxides of kaolinite showed a complex dependence on the relative amounts of several structural oxidizing/reducing entities within the reaction-promoting solids. The rates indicated an important role of the clay but no dominant role of any one of the oxidizing/reducing entities. In this paper we review (a) the reaction-promoting activity of these centers as studied in other systems, (b) various spectroscopic results showing interaction between these entities in clays, and (c) reported spectroscopic studies of the complexation between hydrazine and aluminosilicate surfaces as a whole, in an effort to propose a mechanism for the reaction. Whereas some uncertainties remain, the present synthesis concludes that a mechanism operating through single electron/hole transfers and hydrogen atom transfers by discrete centers is adequate to explain the observed rate behaviors including the observed second order dependence of the oxidation rate on catalyst amount. The effects of these operations on the catalyst can result in no alteration of, or complete or partial electronic relaxation of its contingent of trapped separated charge pairs. The degree to which surface complexation as a whole, intercalation, or luminescent processes may also be associated with the reaction cannot be adequately assessed with the information in hand.

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

Luminescence, induced by dehydration and by wetting with hydrazine and unsymmetrically substituted hydrazine, and related ESR spectra have been observed from several kaolinites, synthetically hydrated kaolinites, and metahalloysites. The amine-wetting luminescence results suggest that intercalation, not a chemiluminescence reaction, is the luminescence trigger. Correlation between hydration-induced luminescence and g = 2 ESR signals associated with O(-)-centres in several natural halloysites, and concurrent diminution of the intensity of both these signal types as a function of aging in two 8.4 angstroms synthetically hydrated, kaolinites, confirm a previously-reported relationship between the luminescence induced by dehydration and in the presence of O(-)-centres (holes, i.e., electron vacancies) in the tetrahedral sheet. Furthermore, the ESR spectra of the 8.4 angstroms hydrate showed a concurrent change in the line shape of the g = 4 signal from a shape usually associated with structural Fe in an ordered kaolinite, to a simpler one typically observed in more disordered kaolinite, halloysite, and montmorillonite. Either structural Fe centres and the O(-)-centres interact, or both are subject to factors previously associated with degree of order. The results question the long-term stability of the 8.4 angstroms hydrate, although XRD does not indicate interlayer collapse over this period. Complex inter-relationships are shown between intercalation, stored energy, structural Fe, and the degree of hydration which may be reflected in catalytic as well as spectroscopic properties of the clays.

The National Aeronautics and Space Administration has begun preparations for the flight of the Mars Observer Mission in the early 1990s. An advanced ground-based study is being conducted on a usefully limited suite of Mars Soil Analog Materials (MarSAM) intended to simulate the aeolian material covering the surface of Mars. A series of variably proportioned iron/calcium smectite clays were prepared from a typical montmorillonite clay using the Banin method. The effect of increasing iron on a diverse set of chemical and spectroscopic properties of the suite of clays is discussed. In order to chemically characterize the MarSAM and compare them with the Martian soil studied by Viking, the clays were analyzed for their major and minor elemental compositions by X-ray fluorescence and ion-coupled plasma techniques. It was concluded that the surface iron has a complex and hitherto uninvestigated impact on the catalytic and spectroscopic properties of clays and on the ability of these material to store energy.

Clays have been implicated in the origin of terrestrial life since the 1950's. Originally they were considered agents which aid in selecting, concentrating and promoting oligomerization of the organic monomeric substituents of cellular life forms. However, more recently, it has been suggested that minerals, with particular emphasis on clays, may have played a yet more fundamental role. It has been suggested that clays are prototypic life forms in themselves and that they served as a template which directed the self-assembly of cellular life. If the clay-life theory is to have other than conceptual credibility, clays must be shown by experiment to execute the operations of cellular life, not only individually, but also in a sufficiently concerted manner as to produce some semblance of the functional attributes of living cells. Current studies are focussed on the ability of clays to absorb, store and transfer energy under plausible prebiotic conditions and to use this energy to drive chemistry of prebiotic relevance. Conclusions of the work are applicable to the role of clays either as substrates for organic chemistry, or in fueling their own life-mimetic processes.

The dehydration-induced luminescence of a colloidal kaolinite is investigated experimentally, with particular attention given to the effect of various treatments on the luminescence characteristics. It is found that the total photon count of the emitted light is linearly related to the film thickness up to a thickness of 30 microns; mechanical stress in the form of grinding increases the photon output and produces extensive changes in the emission kinetics. A direct check of the emission wavelength dependence (by using color filters) indicates that roughly 75 percent of the emission occurs in the wavelength range below 410 nm. It is also found that incorporation of fluorescent molecules into the kaolinite paste increases the photon output and may indicate the transfer of ultraviolet photons to the fluorescent probe.

Several new, room-temperature luminescent phenomena, resulting from the interaction of kaolin and various amino compounds, have been observed. The emission of light from kaolin pastes (treated with quinoline, pyridine, hydrazine, monoethanolamine, n-butylamine, and piperidine) was shown to decay monotonically over a period of hours to days. More light was released by a given amino compound after it was dried and purified. Hydrazine, in addition to the monotonically decaying photon release, produces delayed pulses of light with peak emission wavelength of 365 nm which last between several hours and several days. These photon bursts are acutely sensitive to the initial dryness of the hydrazine, both in the number of bursts and the integrated photon output. The amount of light and the capacity of the kaolin to produce the delayed burst appeared to be strongly dependent on preliminary heating and on gamma-irradiation, analogous to the dehydration-induced light pulse previously reported from the Ames Research Center. A small, delayed burst of photons occurred when piperidine and n-butylamine were removed by evaporation into an H2SO4 reservoir.

Experimental data concerning emission of light upon dehydration as a function of preheating and pre-gamma-irradiation are correlated with reported studies of electron-spin resonance (ESR) activity after similar pretreatments. The effect of these pretreatments on the kaolin-promoted incorporation of glycine into peptide oligomers in a wet/cold, hot/dry fluctuating environment is compared to their effect on the ESR and luminescent signals. The existence of spectroscopically active centers appears to be loosely anticorrelated with reaction yield; these yields are increased by increasing the overall energy content of the material. It is concluded that some part of the chemical yield is produced by a mechanism involving intrinsic, excited electronic states of the clay crystal lattice. These states may be derived from thermally, interfacially, and/or mechanically induced charge reorganization within interspersed energy levels in the band structure of the material.

The decay curves of various triboluminescent-excited materials were obtained, including well-crystallized and poorly crystallized kaolin, bentonite, quartz, sodium chloride, and chalk calcite. A qualitative increase in triboluminescence was observed for kaolin dipped in water or tryptophan solution compared to dry kaolin, and for frozen kaolin and montmorillonite pastes. Theoretical explanations for the tryptophan effect are discussed.

A self-consistent charge extended Hueckel program is used in modeling isomorphic substitution of Al(3+) by Na(+), K(+), Mg(2+), Fe(2+), and Fe(3+) in the octahedral layer of a dioctahedral smectite clay, such as montmorillonite. Upon comparison of the energies involved in the isomorphic substitution, it is found that the order for successful substitution is as follows: Al(3+), Fe(3+), Mg(2+), Fe(2+), Na(+), which is equivalent to Ca(2+), and then K(+). This ordering is found to be consistent with experimental observation. The calculations also make it possible to determine the possible penetration of metal ions into the clay's 2:1 crystalline layer. For the cases studied, this type of penetration can occur at elevated temperatures into regions where isomorphic substitution has occurred with metal ions that bear a formal charge of less than 3+. The computed behavior of the electronic structure in the presence of isomorphic substitution is found to be similar to behavior associated with semiconductors.

Reports of triboluminescent phenomena in organic crystalline materials prompted a search for related processes in clay minerals. The reported extensive mechanical distortion produced on freezing and drying of montmorillonite was particularly interesting because of studies of condensation reactions in a wet/dry cycled reaction sequence. The discovery of an unusual luminescent process in several clay minerals is reported and its characteristics are described.

Clay minerals catalyze peptide bond formation in fluctuating environments. A number of plausible mechanisms have been proposed and tested. The possibility that clays may actually be energizing the reaction by means of electronic excitation, creating mobile or trapped holes and electrons in the lattice, is explored. It has been discovered that clays emit light upon dehydration. The correlation between dehydration-induced, or thermoluminescent, processes and the yield of glycine oligomers after treatments known to affect the luminescent yields is being tested, in an effort to understand the catalytic mechanism