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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Impact-Induced Clay Mineral Formation and Distribution on Mars

Clay minerals have been identified in the central peaks and ejecta blankets of impact craters on Mars. Several studies have suggested these clay minerals formed as a result of impact induced hydrothermalism either during Mars' Noachian era or more recently by the melting of subsurface ice. Examples of post-impact clay formation is found in several locations on Earth such as the Mjolnir and Woodleigh Impact Structures. Additionally, a recent study has suggested the clay minerals observed on Ceres are the result of impact-induced hydrothermal processes. Such processes may have occurred on Mars, possibly during the Noachian. Distinguishing between clay minerals formed preor post-impact can be accomplished by studying their IR spectra. In fact, showed that the IR spectra of clay minerals is greatly affected at longer wavelengths (i.e. mid-IR, 5-25 micron) by impact-induced shock deformation while the near-IR spectra (1.0-2.5 micron) remains relatively unchanged. This explains the discrepancy between NIR and MIR observations of clay minerals in martian impact craters noted. Thus, it allows us to determine whether a clay mineral formed from impact-induced hydrothermalism or were pre-existing and were altered by the impact. Here we study the role of impacts on the formation and distribution of clay minerals on Mars via a fully 3-D Monte Carlo cratering model, including impact- melt production using results from modern hydrocode simulations. We identify regions that are conducive to clay formation and the location of clay minerals post-bombardment.

Rivera-Valentin, E. G.↗
NASA NTRS1992

Preliminary results of an experimental study of the interactions of basalt glass and a water vapor atmosphere: Implications for weathering on Mars

Models of weathering processes on the surface of Mars invoke hydrothermal alteration as the primary mechanism responsible for clay formation. Previous experimental studies of basalt glass interactions with water under hydrothermal conditions demonstrate that phyllosilicates and zeolites are the primary alteration minerals. Gas-solid weathering is thought to be less thermodynamically favorable and relatively unimportant, however, the experimental alteration of basalt glass under vapor ion conditions (large SA/V) can result in the formation of clay minerals, zeolites, and hydrated calcium silicates. We have undertaken a study of the reacted layers formed on basalt glasses experimentally altered under vapor hydration conditions to resolve this issue. High SA/V ratios promote reaction product buildup in solution and promote alteration mineral formation. It was previously shown that these reaction conditions promote weathering processes similar to those found in nature for tektite glasses, rhyolitic glasses, and basalt glasses. The hydration of basalt glass is described for 100 percent relative humidity experiments at temperatures of 150, 175, and 200 C for up to 400 days. Preliminary characterization of the alteration layers with analytical electron and scanning microscopy suggest that the reaction mechanism includes precipitation of a smectite clay on the outermost surface of the glass. Between the clay and the unreacted glass is an amorphous gel-like phase (palagonite). Our results provide an experimental basis for proposing that basalt glass interactions with vapor atmospheres can be an important source of clay minerals.

Mazer, J. J.↗
NASA NTRS1984

Acyl silicates and acyl aluminates as activated intermediates in peptide formation on clays

Glycine reacts with heating on dried clays and other minerals to give peptides in much better yield than in the absence of mineral. This reaction was proposed to occur by way of an activated intermediate such as an acyl silicate or acyl aluminate analogous to acyl phosphates involved in several biochemical reactions including peptide bond synthesis. The proposed mechanism has been confirmed by trapping the intermediate, as well as by direct spectroscopic observation of a related intermediate. The reaction of amino acids on periodically dried mineral surfaces represents a widespead, geologically realistic setting for prebiotic peptide formation via in situ activation.

White, D. H.↗
NASA NTRS1989

Mars, clays and the origins of life

To detect life in the Martian soil, tests were designed to look for respiration and photosynthesis. Both tests (labeled release, LR, and pyrolytic release, PR) for life in the Martian soils were positive. However, when the measurement for organic molecules in the soil of Mars was made, none were found. The interpretation given is that the inorganic constituents of the soil of Mars were responsible for these observations. The inorganic analysis of the soil was best fitted by a mixture of minerals: 60 to 80 percent clay, iron oxide, quartz, and soluble salts such as halite (NaCl). The minerals most successful in simulating the PR and LR experiments are iron-rich clays. There is a theory that considers clays as the first organisms capable of replication, mutation, and catalysis, and hence of evolving. Clays are formed when liquid water causes the weathering of rocks. The distribution of ions such as aluminum, magnesium, and iron play the role of bases in the DNA. The information was stored in the distribution of ions in the octahedral and tetrahedral molecules, but that they could, like RNA and DNA, replicate. When the clays replicated, each sheet of clay would be a template for a new sheet. The ion substitutions in one clay sheet would give rise to a complementary or similar pattern on the clay synthesized on its surface. It was theorized that it was on the surface of replicating iron-rich clays that carbon dioxide would be fixed in the light into organic acids such as formic or oxalic acid. If Mars had liquid water during a warm period in its past, clay formation would have been abundant. These clays would have replicated and evolved until the liquid water was removed due to cooling of Mars. It is entirely possible that the Viking mission detected life on Mars, but it was clay life that awaits the return of water to continue its evolution into life based on organic molecules.

Hartman, Hyman↗
NASA NTRS1991

Field trip guidebook on environmental impact of clays along the upper Texas coast

The field trip was prepared to provide an opportunity to see first hand some the environmental hazards associated with clays in the Houston, Texas area. Because of the very high clay content in area soils and underlying Beaumont Formation clay, Houston is a fitting location to host the Clay Mineral Society. Examinations were made of (1) expansive soils, (2) subsidence and surface faulting, and (3) a landfill located southeast of Houston at the Gulf Coast Waste Disposal Authority where clay is part of the liner material.

Garcia, Theron D.↗
NASA NTRS1982

Experimental shock lithification of water-bearing rock powders

The geology and morphology of the terrestrial planets and their moons have been profoundly affected by impact cratering. Some of these bodies contain substantial quantities of water or ice in their regoliths. It is pointed out that the effects of impacts into water-bearing target rocks are not well understood, and may be significantly different from those produced by identical impacts on a desiccated surface. The present investigation has the objective to determine the effects of water on targets of powdered rock and to seek evidence of impact-induced hydration or clay formation. Samples of andesitic basalt were crushed and sieved, and experiments were conducted on the material smaller than 150 micrometers. These experiments show that the water content of a powdered rock target can strongly affect its physical condition following an impact. A relatively small component (5-15 wt %) of water or ice in planetary surface material could inhibit or prevent lithification throughout much of the shocked volume at an impact site.

Allen, C. C.↗
NASA NTRS2001

Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

We are investigating the weathering of silicate minerals by both purely inorganic, and biologically mediated processes using field-emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectroscopy (EDS). By resolving surface textures and chemical compositions of weathered surfaces at the sub-micron scale we hope to be able to distinguish abiotic from biotic weathering processes and so establish a new biosignature applicable to the study of astromaterials including but not limited to the Martian meteorites. Sterilized olivine grains (San Carlos, Arizona) no more than 1-2 mm in their longest dimension were optically assayed to be uniform in color and free of inclusions were selected as weathering subjects. Prior to all experiments surface morphologies and Fe/Mg ratios were determined for each grain using FE-SEM and EDS. Experiments were divided into two categories abiotic and biotic and were compared with "naturally" weathered samples. For the preliminary experiments, two trials (open and closed to the ambient laboratory environment) were performed under abiotic conditions, and three trials under biotic conditions (control, day 1 and day 2). The open system abiotic trials used sterile grains heated at 98 C and 200 C for both 24 and 48 hours in 1L double distilled de-ionized water. The closed system abiotic trials were conducted under the same conditions but in a sealed two layer steel/Teflon "bomb" apparatus. The biotic trials used sterile grains mounted in a flow-through device attached to a wellhead on the Columbia River aquifer. Several discolored, altered, grains were selected to document "natural" weathering surface textures for comparison with the experimental samples. Preliminary results indicate there are qualitative differences in weathered surface textures among all the designed experiments. The olivine grains in abiotic trials displayed etching, pitting, denticulate margins, dissolution and clay formation. The scale of the features ranged from tens to a few microns with textures that remained relatively sharp and were crystallographically controlled. These results were comparable to that observed in the "naturally" weathered comparison/reference grains. Chemical analysis by EDS indicates these textures correlated with the relative loss of Mg and Fe cations by diffusional processes. In contrast the biotic results indicated changes in the etching patterns on the scale of hundreds of nm, which are neither sharp nor crystallographically controlled (nanoetching). Organisms, organic debris and/or extracellular polymeric substances (biofilm) were often in close proximity or direct contact with the nanoetching. While there are many poorly constrained variables in natural weathering experiments to contend with, such as the time scale, the chemistry of the fluids and degree of biologic participation, some preliminary observations can be made: (1) certain distinct surface textures appear correlated with the specific processes giving rise to these textures; (2) the process of diffusing cations can produce many similar styles of surface textural changes; and (3) the main difference between abiotic and biotically produced weathering is the scale (microns versus nanometers) and the style (crystallographically versus noncrystallographically controlled) of the textural features. Further investigation into nanosize scale surface textures should attempt to quantify both textures and chemical changes of the role of microorganisms in the weathering of silicates. Additional experiments addressing nanoscale textures of shock features for comparison with the current data set.

Longazo, Teresa G.↗
NASA NTRS1981

Enhancement of peptide bond formation by polyribonucleotides on clay surfaces in fluctuating environments

The selective effects of polyribonucleotides on the formation of glycine peptide bonds in glycine on clay surfaces are investigated as a model for a template mechanism for the effects of polynucleotides on peptide bond formation. Free oligoglycine yields were determined for the cycling reaction of glycine in the presence and absence of clay and polyribonucleotides or polydeoxyribonucleotides. The polyribonucleotides are observed to lead to increases of up to fourfold increases in oligoglycine formed, with greater enhancements for poly-G nucleotides than for poly-A, poly-U and poly-C, indicating a codonic bias. Polydeoxyribonucleotides are found to provide no enhancement in peptide formation rates, and yields were also greatly reduced in the absence of clay. A mechanism for peptide synthesis is proposed which involves the activation of glycine on the clay surface, followed by the formation of esters between glycine and the 2-prime OH groups of the polyribonucleotide and peptide bonds between adjacent amino acyl esters. It is pointed out that if this mechanism is correct, it may provide a basis for a direct template translation process, which would produce a singlet genetic code.

White, D. H.↗
NASA NTRS1999

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine

The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

NASA Discipline Exobiology↗
NASA NTRSDate not supplied

Acid Alteration of Clay Minerals With Implication for Mars’ Surface Processes

The co-occurrence of phyllosilicates (clays) and sulfate stratigraphies at many locations on Mars are associated with a sharp change in surface conditions from neutral/alkaline pH during the Noachian (4.1-3.7 Ga) which favored the formation of clays to acidic conditions during the Hesperian (3.7-2.9 Ga) which favored the formation of sulfates. Yet, if these two contrasting geosystems were temporarily sequential, it is unknown how the Hesperian acidic conditions altered the previously formed clay units. We performed laboratory batch experiments to fingerprint the diagnostic features produced during interactions of Mars-analog clays and acidic solutions. Two clays, and silicon (IV) oxide, were reacted with solution of either sulfuric acid or filtered natural acid rock drainage (ARD) in plastic bottles. The solutions were adjusted at four pH values (1, 3, 5, and 7) and reacted at 4, 30, and 80°C for 3, 7, and 14 days. At the end of the experiments, the filtered supernatants were analyzed by ICP-MS while the solids were characterized by X-Ray Diffraction; Energy-Dispersive X-Ray Fluorescence analyses; Raman and Short-Wave Infrared spectroscopies and Scanning Electron Microscopy. Results show that the solution chemistry played a key role in the evolution of the clay-solution systems. In H2SO4 systems, the solution pH steadily increased due to partial clay dissolution with no secondary phase formation detected. Contrary, in the ARD systems, the pH decreased due to the ample presence of Fe which controlled both the reactivity of clays by the growth of protecting surface coatings and the solution pH by the precipitation of Fe nanophases; secondary phase detected included goethite, jarosite, gypsum, and siderite. These results indicate that, on Mars, the chemical interaction between clays and acidic solutions was complex and dependent on the solution chemistry. Acidic, sulfate-rich solutions have a high dissolution capacity and could have induced widespread clay disintegration. Notably, if Fe-rich ARD was involved, the clays on Mars could have remained stable during acidic Hesperian period due to formation of protective coatings. Comparison of our results with martian observations will be performed to determine how acidic conditions could potentially affect clays in sedimentary settings, including the Gale crater.

L. Lefticariu↗
NASA NTRS1979

Prebiotic nucleotide oligomerization in a fluctuating environment - Effects of kaolinite and cyanamide

The clay kaolinite was tested for its ability to promote nucleotide oligomerization in model prebiotic systems. Heterogeneous mixtures of clay, water and nucleotide were repeatedly evaporated to dryness at 60 C and redissolved in water in cyclic fashion in the presence or absence of cyanamide and/or ammonium chloride. With or without cycling, kaolinite alone did not promote the oligomerization of nucleotides at detectable levels. Cycling of clay in combination with cyanamide, however, promoted high levels of condensation to a mixture of oligonucleotides and dinucleotide pyrophosphate without requiring ammonium chloride. Although cycling with clay favored synthesis of dinucleotide pyrophosphate, cycling without clay enhanced formation of oligonucleotides. These results support the hypothesis that the presence of clays in fluctuating environments would have influenced the course of prebiotic condensation reactions.

Odom, D. G.↗
NASA NTRS2017

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

The CheMin XRD instrument aboard Mars Science Laboratory (MSL) has documented clay minerals in various drill samples during its traverse of Gale Crater's floor and ascent of Mt. Sharp. The most recent samples, named Marimba, Quela and Sebina were acquired from the Murray Formation in the Murray Buttes region of lower Mt. Sharp. Marimba and Quela come from a approx. 30 m package of finely laminated lacustrine mudstones. Sebina comes from an overlying package of heterolithic mudstone-sandstones. Clay minerals make up approx.15-25 wt.% of the bulk rock with similar contributions to XRD patterns in all three samples. Broad basal reflections at approx. 10deg 2(theta) CoK(alpha) indicate the presence of 2:1 group clay minerals. The 02(lambda) clay mineral band lies at approx. 22.9deg 2(theta), a region typically occupied by Fe-bearing dioctahedral 2:1 clay minerals like nontronite or Fe-illite. The low humidity within the CheMin instrument, which is open to the martian atmosphere, promotes loss of interlayer H2O and collapse of smectite interlayers making them difficult to distinguish from illites. However, based on the low K content of the bulk samples, it appears that smectitic clay minerals are dominant. Peak dehydroxylation of the Marimba sample measured by the SAM instrument on MSL occurred at 610C and 780C. Fe-bearing smectites are not consistent with these dehydroxylation temperatures. Thus, we suggest that a mixture of dioctahedral and trioctahedral smectite phases are present giving the appearance of intermediate octahedral occupancy in XRD. Dioctahedral smectites have not previously been reported in Gale Crater by MSL. Earlier in the mission, relatively clay mineral rich samples (approx. 20 wt.%) from lacustrine mudstones in Yellowknife Bay (YKB) were found to contain ferrian saponites. It is proposed that YKB saponites formed via isochemical aqueous alteration of detrital olivine close to the time of sediment deposition, under anoxic to poorly oxidizing conditions. In terrestrial settings where alteration sequences of basaltic rocks or sediments are observed, first-stage alteration clay minerals are typically trioctahedral smectite species, as reported from YKB. In later alteration stages trioctahedral clay minerals are replaced by dioctahedral clays as a result of removal and/or oxidation of Fe2+ and Mg. Observed changes in clay mineralogy between YKB and Murray Buttes samples correspond with differences in bulk mineralogy, including: 1) a transition from magnetite to hematite as the main Fe-oxide, 2) increasing abundances of Ca-sulfates and 3) a reduction in the quantity of reactive mafic minerals. This mineralogical change indicates an increasing degree of aqueous alteration and oxidation of mafic detritus in the upper part of the Murray Formation. These results broaden the spectrum of mineralogical facies documented by MSL. Together sedimentology and mineralogy indicate a long-lasting, dynamic fluvial-lacustrine system encompassing a range aqueous geochemical processes under varying redox conditions. Future work is needed to unravel the influence of global and local controls on the range of ancient conditions observed at Gale Crater.

MSL↗
NASA NTRS1976

Clays as possible catalysts for peptide formation in the prebiotic era

From the point of view of prebiotic synthesis, clays might have performed functions of concentration, catalysis, and protection of molecules. The degrees of polymerization obtained, when amino acid adenylates are added to montmorillonite suspensions in water, are much higher than those obtained by polymerization in the absence of such a clay. In addition, they are of a discrete spectrum, usually multiples of 6 or 7, and reach values of up to 40 mers. In the absence of clay a continuous spectrum of degrees of polymerization is obtained, and usually up to 4-6 mers only. Copolymerization in the absence of clays yields mostly random copolymers, in their presence mostly block copolymers are obtained. Optical density measurements show that after adsorption has taken place on the clay, stacking of its layers occurs. Polymerization starts only after these stacked layers have been formed

Paecht-Horowitz, M.↗
NASA NTRS1989

Soil developments in polar deserts: Implications for exobiology and future Mars missions

Chemical alterations, weathering, and diagenesis of soil profiles from the dry valleys of Antarctica were studied as analogs of regolith development for the Martian regolith. Chemical weathering processes play an important part in soil development within the dry valleys of Antarctica. A suite of core samples were studied which were taken within the valley floors in addition to samples taken in the vicinity of evaporite and brine ponds. Analysis of water soluable cations and anions from core samples were performed along with petrographic analysis of selected samples. It was shown that ionic transport processes operate primarily above the permafrost zone. Abundances of the water soluable ions reflect the nature of secondary minerals produced by evaporation and weathering. Chloride, calcium, and sodium abundances for soils from the cores within the North and South Forks of Wright Valley, reflect the secondary mineralogy of the soil columns. Calculations for Na, Ca, and Cl abundances reflect the appearance of halite and antarcticite. In areas where excess Ca is present, X-ray diffraction studies show the presence of gypsum. It is well known that the Martian surface conditions may be favorable for chemical weathering. Primary silicates would be expected to be reactive with any ground water. It seems likely that Martian subsurface water is available to assist in the weathering of the primary minerals. Such weathering could result in the formation of clays, sulfates, carbonates, hydrates, halides, and zeolites. The dry valley cores have shown that they maybe excellent analogs to weathering processes on the near-surface of Mars. Since movement of water within the near-surface region clearly results in chemical weathering, leaching, and salt formation in the dry valleys, similar processes are probably operating within the Martian regolith.

Gibson, Everett K., Jr.↗
NASA NTRS1988

Theoretical investigation of the role of clay edges in prebiotic peptide bond formation. II - Structures and thermodynamics of the activated complex species

Molecular orbital calculations are used to study amino acid activation by anhydride formation in neutral phosphates and in tetrahedral silicate and aluminate sites on clay edges. The results agree with previous ab initio studies of Luke et al. (1984) on the reactant species. Relative heats of formation of the anhydrides indicate the extent of anhydride formation to be the greatest for Al and the least for phosphate, which is the same order as the stability of hydrolysis.

Collins, Jack R.↗
NASA NTRSDate not supplied

New Mastcam Multispectral Rock Classes in Sulfate-Bearing Strata, Gale Crater, Mars

Orbital data of Gale Crater, Mars has identified a transition in the stratigraphy of Mt. Sharp indicating an environmental change from a wetter one that accommodated clay mineral formation to a drier environment that led to the precipitation of sulfates. Mt. Sharp is not the only location on Mars for which this transition has been observed which suggests a global environmental change around the Noachian-Hesperian transition. Also visible from orbit is a dark-toned marker band that lies within the sulfate-bearing strata hypothesized to be a volcanic ash deposit. The Mars Science Laboratory (MSL) Curiosity rover is currently exploring this region of Mt. Sharp. In-situ analyses by the rover show changes in morphology and chemistry between the sulfate-bearing layers below and above the marker band and the marker band itself. The MSL instrument payload includes the Mast Camera (Mastcam), which collects multispectral images to provide context for other instruments and broad mineralogic interpretations. In addition to mafic Fe-bearing minerals, Mastcam is sensitive to oxides and some hydrated minerals, important indicators of alteration. In our previous work, we compiled a database of Mastcam spectra through Curiosity’s exploration of Vera Rubin ridge (sols 0-2302), from which 9 spectral classes of rocks were identified (Fig. 1D). Each class has diagnostic spectral features that reflect a common mineralogic interpretation. More recently, as Curiosity traversed through the clay-rich region, Glen Torridon (GT), there was some variation in the rock spectral classes potentially due to nontronite and other phyllosilicates, but not enough to warrant new spectral classes (Fig. 1B). We hypothesize that new classes will appear in accordance with sulfate-bearing strata and the marker band, specifically appearing as a ‘downturn’ in the last two wavelength filters that is inherent, but not unique, to polyhydrated Mg-sulfates. Here, we expand upon our analysis of Mastcam multispectral observations through Curiosity’s second encounter with the marker band (up to sol 3672), comparing the spectral diversity within the sulfate-bearing unit and the marker band to the spectral classes encountered previously in the traverse. These analyses will provide a basis for comparison and aid in selecting targets for in-situ investigations as Curiosity continues its ascent of Mt. Sharp.

A M Eng↗
NASA NTRS1974

The formation of goethite and hydrated clay minerals on Mars

Laboratory studies reported by Huguenin (1973) on the kinetics and mechanism of the photostimulated oxidation of magnetic and preliminary laboratory data on the weathering of silicates, reported herein, are applied to Mars. Basalts in the Martian dark areas are predicted to alter to hydrated Fe(2 plus or minus) depleted clay minerals, minor goethite, and minor to trace amounts of transition metal oxides such as TiO2, MnO2, and Cr2O3 at a rate of 10 to the minus 1.5 plus or minus 1.5 micron/yr. Some Ca-Mg carbonates are also expected to be formed. The clay minerals are predicted to be more silica-rich than the silicate source material, SiO2 contents of 60% or higher being expected, and strongly depleted in Fe(2+). The oxygen, OH, and H2O contents of the bulk weathering product are predicted to be significantly greater than those of the dark-area source materials, whereas the relative bulk metal abundances should be the same.

Huguenin, R. L.↗