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Smectite (e.g., Montmorillonite): phyllosilicate minerals found in bentonites. Bentonites have been considered as key backfill barrier materials in deep geological nuclear waste repository concepts. Swelling/shrinking of montmorillonite (MMT) occurs with increasing/decreasing relative humidity. Microscopically, how does the hydration/dehydration process occur?
Thermodynamic calculations show that, under present Martian surface conditions, favorable gas-solid weathering products of feldspar glasses should include beidellites (clays of the montmorillonite series) + carbonates + quartz. The gas-solid weathering of mafic silicate glass ( of volcanic or impact origin) may similarly favor the production of metastable Fe-rich montmorillonite clays. Simple mass-balance calculations suggest that gas-solid weathering of Martian proto-regolith containing 10% glass could conceivably produce a global blanket of clays at a rate of at least 0.4 cm/b.y. The production rate should be expected to increase significantly with the glass content and rate of reworking of the proto-regolith and with the availability of water. Complete extraction of altered glass from a lunar-like proto-regolith might yield a global Martian clay blanket about 10-100 cm in thickness.
Medium spectral resolution (20 kaysers) infrared measurements of the Martian disk made between 2900 and 5600 kaysers from the NASA Lear Airborne Observatory have been successfully compared with predictions derived from a model of the Martian soil and atmosphere. Modeling of the Martian atmosphere permitted the extraction of Martian soil reflectance in the CO2 bands centered at 3657 kaysers. Three Martian soil analogs previously considered acceptable - limonite, montmorillonite, and basalt - were analyzed to determine the optical complex indices of refraction in the same range as the airborne observations, for mathematical modeling. A characteristic surface particle size approximately 1 to 3 microns diameter is indicated. It is concluded that the Martian soil surface near-infrared optical properties are consistent with a soil composition similar to montmorillonite or limonite, mixed with a basalt.
Montmorillonite clays which contain Fe(III) inhibit the oligomerization of aqueous solutions of HCN. The inhibitory effect is due to the rapid oxidation of diaminomaleonitrile, a key intermediate in HCN oligomerization, by the Fe(III) incorporated into the aluminosilicate lattice of the clay. The Fe(III) oxidizes diaminomaleonitrile to diiminosuccinonitrile, a compound which is rapidly hydrolyzed to HCN and oxalic acid derivatives. Diaminomaleonitrile is not oxidized when Fe(III) in the montmorillonite is reduced with hydrazine. The oxidation state of the clay is an important variable in experiments designed to simulate clay catalysis on the primitive earth.
Samples of various clays and minerals were ground or fractured and monitored with a liquid scintillation spectrometer in order to obtain triboluminescent decay curves. Kaolinite samples displayed several million counts/min after grinding, with a surface area emission estimated at tens of billions of photons/sq cm of surface. The photon production rates varied with the origin of the sample, and kaolinite continually yielded higher production rates than bentonite. The addition of water to the samples slightly increased the count rate of emitted light, while the addition of the fluorescent molecule substance tryptofan significantly enhanced the count rate. Freezing smears of kaolinite and montmorillonite in liquid nitrogen and in a salt ice mixture also induced triboluminescence in the montmorillonite. A possible connection between powdery triboluminescent materials formed in mining industries and respiratory disorders among miners is suggested.
The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.
The Shuttle Multispectral Infrared Radiometer (SMIRR) is a spectroradiometer covering the region from 0.5 to 2.5 microns in 10 channels that acquired data from spots 100 m in diameter along the subspacecraft ground track. It was flown aboard the second flight of the Space Shuttle Columbia, November 12-14, 1981. Data collected during orbit 16 over southern Egypt show that carbonate rocks, kaolinite, and possibly montmorillonite can be identified by their SMIRR spectral signatures and limited knowledge of the lithologic units present. Detailed analysis of SMIRR data for this area indicates that calcite, kaolinite, and montmorillonite rocks give rise to absorption features that result in characteristic 10 channel spectra.
Three flight lines of Airborne Imaging Spectrometer (AIS) data were collected in 128 bands between 1.2 and 2.4 microns in the Hot Creek Range, Nevada on July 25, 1984. The flight lines are underlain by hydrothermally altered and unaltered Paleozoic carbonates and Tertiary rhyolitic to latitic volcanics in the Tybo mining district. The original project objectives were to discriminate carbonate rocks from other rock types, to distinguish limestone from dolomite, and to discriminate carbonate units from each other using AIS imagery. Because of high cloud cover over the prime carbonate flight line and because of the acquisition of another flight line in altered and unaltered volcanics, the study has been extended to the discrimination of alteration products. In an area of altered and unaltered rhyolites and latites in Red Rock Canyon, altered and unaltered rock could be discriminated from each other using spectral features in the 1.16 to 2.34 micron range. The altered spectral signatures resembled montmorillonite and kaolinite. Field samples were gathered and the presence of montmorillonite was confirmed by X-ray analysis.
Changes in the degree of isomerization of steranes and triterpanes during kerogen pyrolysis in the absence or presence of minerals are described. Kerogen from a Monterey Formation diatomite core sample was pyrolyzed under reduced pressure at 300 C for 2-1000 hrs in the presence or absence of calcite, illite, and montmorillonite. It is observed that the extent of isomerization of biomakers in C-20 in 14 alpha(H), 17 alpha(H)-steranes, at C-22 in 17 alpha(H), 21 beta(H)-hopanes and of 17 beta(H), 21 beta(H)-hopanes correlates to early diagenetic stages in rock extracts from sedimentary basins, and faster isomerization for steranes and triterpanes in the bitumen then for those in the kerogen structure are detected. The effects of the minerals on the isomerization reactions are examined; calcite inhibits, and illite and montmorillonite catalyze the reactions.
Airborne Imaging Spectrometer (AIS) data, field and laboratory spectra and samples for X-ray diffraction analysis were collected in argillically altered Tertiary volcanic rocks in the Hot Creek Range, Nevada. From laboratory and field spectral measurements in the 2.0 to 2.4 micron range and using a spectroradiometer with a 4 nm sampling interval, the absorption band centers for kaolinite were loacted at 2.172 and 2.215 microns, for montmorillonite at 2.214 micron and for illite at 2.205. Based on these values and the criteria for resolution and separtion of spectral features, a spectral sampling interval of less than 4 nm is necessary to separate the clays. With an AIS spectral sampling interval of 9.3 nm, a spectral matching algorithm is more effective for separating kaolinite, montmorillonite, ad illite in Hot Creek Range than using the location of absorption minima alone.
The state and distribution of H2O molecules at high latitudes are evaluated numerically with emphasis on the effects of seasonal temperatures on the kinetics of H2O transport. The investigation is carried out with a thermal model for the regolith regions from the surface through the ice interface and an atmospheric model for the H2O vapor density at the surface as a function of latitude. Few differences are found in the state and distribution of H2O whether the regolith is composed of Montmorillonite or basalt. During an obliquity cycle, the average exchanged H2O mass is determined to be in the range 1-20 gr/sq cm over the planetary surface, with a total maximum exchanged volume of 1500 cu km of H2O. The exchanged mass would arise mainly from ground ice in the case of a basalt regolith and from adsorbed H2O with Montmorillonite. Finally, seasonal ice stabilization is expected to occur at latitudes above 40 deg when obliquities exceed 25 deg.
The effect of common sedimentary minerals (illite, Na-montmorillonite, or calcite) under different water concentrations on the generation and release of n-alkanes, acyclic isoprenoids, and select alkenes from oil-prone kerogens was investigated. Matrices containing Green River Formation kerogen or Monterey Formation kerogen, alone or in the presence of minerals, were heated at 200 or 300 C for periods of up to 1000 hours, and the pyrolysis products were analyzed. The influence of the first two clay minerals was found to be critically dependent on the water content. Under the dry pyrolysis conditions, both minerals significantly reduced alkene formation; the C12+ n-alkanes and acyclic isoprenoids were mostly destroyed by montmorillonite, but underwent only minor alteration with illite. Under hydrous conditions (mineral/water of 2/1), the effects of both minerals were substantially reduced. Calcite had no significant effect on the thermal evolution of the hydrocarbons.
The paper presents the results of pyrolysis experiments which were carried out on Green River and Monterey Formation kerogens with and without calcite, illite, or montmorillonite at 300 C for 2 to 1,000 hours under dry and hydrous conditions. The data reveal significant differences in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion of the generated bitumen. In the case of calcite, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible.
A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite (M) and illite, to a lesser extent, alter bitumen during dry pyrolysis. M and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of M and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.
The 5-25 micron real and imaginary refraction indices are presented for palagonite and the silicates pyrophyllite, kaolinite, serpentine, montmorillonite, saponite, and orthopyroxene. Optical constants in the region of the H2O-bending fundamental near 6 microns are obtained for saponite, montmorillonite, and palagonite. It is established that, if a pellet of pure material can be polished to a mirror finish, the optical constants of such noncohesive materials as clays are easily derivable.
The survival of Baccillus subtilis, Azotobacter chroococcum, and the enteric bacteriophage MS2 has been examined in clays representing terrestrial (Wyoming type montmorillonite) and Martian (Fe3+ montmorillonite) soils exposed to terrestrial and Martian environmental conditions of temperature and atmospheric composition and pressure. An important finding is that MS2 survived simulated Mars conditions better than the terrestrial environment, probably owing to stabilization of the virus caused by the cold and dry conditions of the simulated Mars environment. This finding, the first published indication that viruses may be able to survive in Mars-type soils, may have important implications for future missions to Mars.
Laboratory studies of Mars soil analogs pose unique problems, since soils interact readily with their environment and exhibit variable characteristics depending on the environment. We have performed a series of experiments focusing on the spectral properties of clays and how they vary as a function of composition and environment, including examination of fundamental as well as overtone absorptions, that occur in the mid- and near-IR, respectively. Smectite clays have been selected in our laboratory experiments as a primary surface analog for Mars because of their compatibility with results of the Viking biology experiments, their stability under current martian conditions, and their compatibility with reflectance spectra of Mars. We prepared a number of monoionic montmorillonites in order to examine the influence of cations on the water molecules in the clay interlayer region. Moessbauer spectra of several montmorillonites with variable amounts of interlayer iron confirm the presence of ferrihydrite.
We have modified a doubling-and-adding code to reanalyze the Mariner 9 IRIS spectra of Mars atmospheric dust as well as Viking IRTM EPF sequences in the 7, 9, and 20 micron channels. The code is capable of accurate emission/ absorption/scattering radiative transfer calculations over the 5-30 micron wavelength region for variable dust composition and particle size inputs, and incorporates both the Viking IRTM channel weightings and the Mariner 9 IRIS wavelength resolution for direct comparisons to these datasets. We adopt atmospheric temperature profiles according to the algorithm of Martin (1986) in the case of the Viking IRTM comparisons, and obtained Mariner 9 IRIS temperature retrievals from the 15 micron CO2 band for the case of the IRIS comparisons. We consider palagonite as the primary alternative to the montmorillonite composition of Mars atmospheric dust, based on several considerations. Palagonite absorbs in the ultraviolet and visible wavelength region due to its Fe content. Palagonite is also, in principal, consistent with the observed lack of clays on the Mars surface. Furthermore, palagonite does not display strong, structured absorption near 20 microns as does montmorillonite (in conflict with the IRIS observations). We propose that a palagonite composition with particle sizes roughly one-half that of the Toon et al. (1977) determination provide a much improved model to Mars atmospheric dust. Since palagonite is a common weathering product of terrrestrial basalts, it would not be unreasonable for palagonite to be a major surface component for Mars. The lack of even a minor component of Al-rich clays on the surface of Mars could be consistent with a palagonite composition for Mars dust if the conditions for basalt weathering on Mars were sufficiently anhydrous. Variations in palagonite composition could also lead to the inability of the modeled palagonite to fit the details of the 9 micron absorbtion indicated by the IRIS observations.