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NASA NTRS2021

Synthesis and Characterization of Fe(III)-Fe(II)- Mg- Al Smectite Solid Solutions and Implications for Planetary Science

This study demonstrates the synergies and limits of multiple measurement types for the detection of smectite chemistry and oxidation state on planetary surfaces to infer past geochemical conditions. Smectite clay minerals are common products of water-rock interactions throughout the solar system, and their detection and characterization provides important clues about geochemical conditions and past environments if sufficient information about their composition can be discerned. Here, we synthesize and report on the spectroscopic properties of a suite of smectite samples that span the intermediate compositional range between Fe(II), Fe(III), Mg, and Al end-member species using bulk chemical analyses, X-ray diffraction, Vis/IR reflectance spectroscopy, UV and green-laser Raman spectroscopy, and Mössbauer spectroscopy. Our data show that smectite composition and the oxidation state of octahedral Fe can be reliably identified in the near infrared on the basis of combination and fundamental metal-OH stretching modes between 2.1–2.9 μm, which vary systematically with chemistry. Smectites dominated by Mg or Fe(III) have spectrally distinct fundamental and combination stretches, whereas Al-rich and Fe(II)-rich smectites have similar fundamental minima near 2.76 μm, but have distinct combination M-OH features between 2.24 and 2.36 μm. We show that with expanded spectral libraries that include intermediate composition smectites and both Fe(III) and Fe(II) oxidation states, more refined characterization of smectites from MIR data is now possible, as the position of the 450 cm–1 absorption shifts systematically with octahedral Fe content, although detailed analysis is best accomplished in concert with other characterization methods. Our data also provide the first Raman spectral libraries of smectite clays as a function of chemistry, and we demonstrate that Raman spectroscopy at multiple excitation wavelengths can qualitatively distinguish smectite clays of different structures and can enhance interpretation by other types of analyses. Our sample set demonstrates how X-ray diffraction can distinguish between dioctahedral and trioctahedral smectites using either the (02,11) or (06,33) peaks, but auxiliary information about chemistry and oxidation state aids in specific identifications. Finally, the temperature-dependent isomer shift and quadrupole splitting in Mössbauer data are insensitive to changes in Fe content but reliability differentiates Fe within the smectite mineral structure.

Valerie K Fox↗

NASA NTRS2022

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe3+/ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. These experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history. Plain Language Summary: Martian mineral assemblages observed with orbiters and rover instruments allow us to understand the planet's past climate and aqueous activity. Hydrated minerals that contain Fe(II) are of particular interest as they would have been affected by the early atmosphere becoming more oxidizing overtime, changing the structural iron into Fe(III). In this study, we synthesized Fe(II) smectites with varying iron content and irradiated them with an ultraviolet (UV) light source to test whether they could be photooxidized. Iron in the smectite minerals was incompletely oxidized by UV radiation after being exposed for the equivalent of approximately 7 years of exposure on the early Mars surface. The smectites with higher iron content showed more changes with photooxidation in their visible/near infrared spectra as well as in their X-ray diffraction patterns, two datasets collected by instruments on currently active Martian missions. These results suggest that UV photooxidation is a plausible contributor to the mineralogy and redox state of clay mineral assemblages observed at the Martian surface.

V. B. Rivera Banuchi↗

NASA NTRSDate not supplied

Using Mineralogy to Interpret Martian Geologic History

The surface mineralogy of Mars is key to interpreting the planet’s geologic history and constraining when and where Mars may have been habitable to microbial life. Orbital mineralogical data from infrared spectrometers collected over the last two decades have demonstrated that Mars is more than a basaltic planet. Thermal infrared (TIR) emission spectrometers have identified regional variations in igneous minerals, iron oxides, and chloride salts, showing evidence for magmatic evolution and aqueous alteration. Orbital visible/shortwave infrared reflectance spectra provide detailed information about the aqueous history of Mars through the identification of clay minerals, sulfates, carbonates, zeolites, and amorphous materials in ancient ~3-4-billion-year-old terrains. Mineralogical data from rovers allow us to better characterize mineral formation mechanisms by identifying mineral assemblages and placing them in geologic context using outcrop- to grain-scale images. TIR and Mössbauer data from the Mars Exploration Rovers helped identify an ancient dune-interdune playa environment with multiple episodes of groundwater at Meridiani Planum and volcanism-induced hydrothermalism at Gusev crater. The CheMin X-ray diffractometer on the Mars Science Laboratory Curiosity rover in Gale crater is the first fully quantitative mineralogical instrument sent to another planetary surface. CheMin data allow the quantification of minerals and X-ray amorphous materials with a mineral detection limit of <1 wt.% and provide crystal chemistry of major phases from refined unit-cell parameters. CheMin has revealed local mineralogical changes in ancient sedimentary rocks not seen from orbit and helped identify habitable environments. Throughout the 600+ m of vertical stratigraphy studied so far, changes in clay mineralogy, Fe-oxides/oxyhydroxides, sulfates, and carbonates demonstrate a long history of surface and groundwater at Gale crater with variable salinity, pH, Eh, and temperature. Recent CheMin data document a decrease in clay minerals and an increase in sulfate minerals in younger strata that corresponds with a change from fluvio-lacustrine to eolian depositional environments, potentially documenting a change to a drier climate across the planet.

E. B. Rampe↗

NASA NTRS2026

Scientific Highlights and Status of the Mars Science Laboratory Mission, Years 9 through 12

We present the scientific highlights and status from years 9-12 of NASA’s Mars Science Laboratory mission, with its Curiosity rover. A thermochemolysis-based sample analysis revealed a variety of organic molecules preserved in clay mineral-rich lake/lake margin deposits of the Glen Torridon region. The stratigraphically higher clay-sulfate mineral transition on Aeolis Mons was found to be associated with a lithological change from lacustrine to dry aeolian depositional environments. Water intermittently returned to the surface after the increase in aridity, including during the deposition of wave ripple strata which indicate a climate capable of sustaining an ice-free lake in the early Hesperian. The overlying Mg sulfate-bearing unit has both poly- and monohydrated Mg sulfates and is also enriched in iron carbonate of a purity consistent with chemical sedimentation and therefore atmospheric sequestration. A channel-incised canyon within Gediz Vallis and distal alluvial deposits recorded numerous fluvial and debris flow events after the deposition, lithification, and erosion of the clay- and sulfate-bearing units. Bright clasts found in Gediz Vallis canyon are composed of native sulfur. The investigation of the modern atmosphere and environment focused on the influence of the crater and mountain topography and captured high-altitude noctilucent and iridescent clouds. Radiation monitoring now spans an 11-year solar cycle. Rover systems and science instruments remain capable of addressing mission scientific objectives. All ten scientific instruments continue to return high-value data despite degradation of the Chemistry and Camera instrument’s high-voltage system, loss of multispectral imaging capability, and loss of active neutron spectroscopy. The mission has mitigated the loss of redundant brakes on two arm joints, additional wheel wear, and highly reduced capability of the redundant flight computer. Efficiency improvements in rover energy utilization and operations staffing have allowed the mission team to maintain a high level of productivity despite declining rover power generation and funding.

Mars↗

NASA NTRS1985

Air shower arrival directions measured at Buckland Park

The Buckland Park air shower array was operated for 3 years from 1979 to 1981 particularly for the study of anisotropies in the region of the knee of the size spectrum. The array which has been described in detail elsewhere was situated at a latitude of 35 S and had an effective size threshold of approx 3 x 10 to the 5th power particles (approx 3 x 10 to the 15th power Ev for vertical showers). A number of results from this experiment have already been published including anisotropy analyses (Gerhardy and Clay, 1983) and searches for very high energy gamma ray sources. The final distribution of measured shower arrival directions are presented here. These 1.3 x 10 to the 5th power events were selected as indicated in detail in Gerhardy and Clay (1983) and were essentially those events with well measured arrival directions. They are the same data set used in the above reference but no complete sky map has previously been presented.

Gerhardy, P. R.↗

NASA NTRS2022

Biological Oxidation of Fe(II)-Bearing Smectite by Microaerophilic Iron Oxidizer Sideroxydans lithotrophicus Using Dual Mto and Cyc2 Iron Oxidation Pathways

Fe(II) clays are common across many environments, making them a potentially significant microbial substrate, yet clays are not well established as an electron donor. Therefore, we explored whether Fe(II)-smectite supports the growth of Sideroxydans lithotrophicus ES-1, a microaerophilic Fe(II)-oxidizing bacterium (FeOB), using synthesized trioctahedral Fe(II)-smectite and 2% oxygen. S. lithotrophicus grew substantially and can oxidize Fe(II)-smectite to a higher extent than abiotic oxidation, based on X-ray near-edge spectroscopy (XANES). Sequential extraction showed that edge-Fe(II) is oxidized before interior-Fe(II) in both biotic and abiotic experiments. The resulting Fe(III) remains in smectite, as secondary minerals were not detected in biotic and abiotic oxidation products by XANES and Mössbauer spectroscopy. To determine the genes involved, we compared S. lithotrophicus grown on smectite versus Fe(II)-citrate using reverse-transcription quantitative PCR and found that cyc2 genes were highly expressed on both substrates, while mtoA was upregulated on smectite. Proteomics confirmed that Mto proteins were only expressed on smectite, indicating that ES-1 uses the Mto pathway to access solid Fe(II). We integrate our results into a biochemical and mineralogical model of microbial smectite oxidation. This work increases the known substrates for FeOB growth and expands the mechanisms of Fe(II)-smectite alteration in the environment.

smectite↗

NASA NTRS1965

Rugged pressed disk electrode has low contact potential

Pressed-disk electrode with low contact potential monitors physiological processes. It consists of silver and silver chloride combined with bentonitic clay. The clay affords a surface that permits use over extended periods without contact deterioration.

Day, J. L.↗

NASA NTRS1973

Studies of the inner shelf and coastal sedimentation environment of the Beaufort Sea from ERTS-1

The author has identified the following significant results. Northward flowing rivers of Alaska inundate extensive areas of sea ice during spring breakup. This process has been studied under the ERTS-1 program. Drainage of large volumes of fresh water through the ice at holes and cracks (strudel) causes scour depressions, over 4 m deep, and up to 20 m across in the sea floor below. Strudel scours occur within 30 km of river mouths, generally in areas where ERTS-1 imagery shows less potential for drifting ice to scour the bottom than elsewhere. The shapes and distribution patterns of strudel scours correspond with those of strudel seen in the ice canopy. Densities of scours are highest in the inner areas of overlfow. But strudel scours also occur outside of overflow areas mapped during the last several years. These must be very old. One strudel scour investigated by diving is surrounded by a rim, has vertical walls exposing a tundra horizon, and terminates at a gravel layer 4 m below the lagoon floor. Another terminates at a semi-consolidated layer of silty clay. The gravel and silty clay are pre-Holocene deposits. Mixing of Holocene marine with older sediments by vertical strudel flow causes great variability in sediment types over small areas. These observations complicate interpretation of shallow water deposits of cold climates.

Reimnitz, E.↗

NASA NTRS1974

Heat flow and geothermal potential of the East Mesa KGRA, Imperial Valley, California

The East Mesa KGRA (Known Geothermal Resource Area) is located in the southeast part of the Imperial Valley, California, and is roughly 150 kilometers square in areal extent. A new heat flow technique which utilizes temperature gradient measurements across best clays is presented and shown to be as accurate as conventional methods for the present study area. Utilizing the best clay gradient technique, over 70 heat flow determinations have been completed within and around the East Mesa KGRA. Background heat flow values range from 1.4 to 2.4 hfu (1 hfu = .000001 cal. per square centimeter-second) and are typical of those throughout the Basin and Range province. Heat flow values for the northwest lobe of the KGRA (Mesa anomaly) are as high as 7.9 hfu, with the highest values located near gravity and seismic noise maxima and electrical resistivity minima. An excellent correlation exists between heat flow contours and faults defined by remote sensing and microearthquake monitoring.

Swanberg, C. A.↗

NASA NTRS1977

Particle size and X-ray analysis of Feldspar, Calvert, Ball, and Jordan soils

Pipette analysis and X-ray diffraction techniques were employed to characterize the particle size distribution and clay mineral content of the feldspar, calvert, ball, and jordan soils. In general, the ball, calvert, and jordan soils were primarily clay size particles composed of kaolinite and illite whereas the feldspar soil was primarily silt-size particles composed of quartz and feldspar minerals.

Chapman, R. S.↗

NASA NTRS1977

Investigations using data from LANDSAT-2

The author has identified the following significant results. LANDSAT imageries of Mirpur area of Dacca district were used in connection with surveys for black plastic clay. The imageries showed the broad pattern of small valleys cutting into Madhupur clay. Land use maps of Haor areas of Sylhet and Mymensingh districts were prepared. As a test case, two thana areas, namely Nickley and Astogram, were classified in different categories such as crop, settlement, and water. It does not show much agreement with the Agriculture Dept.'s statistics.

Hossain, A.↗

NASA NTRS1977

Geomorphic and landform survey of Northern Appennine Range (NAR)

The author has identified the following significant results. An approach to landslide hazard detection was developed through the analysis of satellite imagery (LANDSAT 2) showing many landslide areas that occur on marine silts and clays in northern Appennine Range in Italy. A landslide risk score was given for large areas by narrowing and extending well defined areas, whose behavior and reflectivity variation was due to upper surface changes. Results show that this methodology allows evolution pattern of clay outflows to be distinguished.

Marino, C. M.↗

NASA NTRS1977

Investigations using data from LANDSAT-2

The author has identified the following significant results. A land use map was prepared of Dacca-Narayanganj-Demra area on a scale of 1:50,000. LANDSAT imageries of Dinajpur and Rangpur districts were studied. The difference between the exposed Pleistocene red clay, this clay under alluvial cover, and recent alluvium were noted. Different types of soils, crops, etc. were delineated on the ERTS imagery.

Hossain, A.↗

NASA NTRS1978

Implications of abundant hygroscopic minerals in the Martian regolith

Converging lines of evidence suggest that a significant portion of the Martian surface fines may consist of salts and smectite clays. Salts can form stoichiometric hydrates as well as eutectic solutions with depressed freezing points; clays contain bound water of constitution and adsorb significant quantities of water from the vapor phase. The formation of ice may be suppressed by these minerals in some regions on Mars, and their presence in abundance would imply important consequences for atmospheric and geologic processes and the prospects for exobiology.

Clark, B. C.↗

NASA NTRS1979

Impact cratering calculations. Part 1: Early time results

Early time two dimensional finite difference calculations of laboratory scale hypervelocity impact of 0.3 g spherical 2024 aluminum projectiles into homogeneous plasticene clay targets were performed. Analysis of resulting material motions showed that energy and momentum were coupled quickly from the aluminum projectile to the target material. In the process of coupling, some of the plasticene clay target was vaporized while the projectile become severely deformed. The velocity flow field developed within the target was shown to have features similar to those found in calculations of near surface explosion cratering. Specific application of Maxwell's analytic Z-Model showed that this model can be used to describe the early time flow fields resulting from the impact cratering calculations as well, provided the flow field centers are located beneath the target surface and most of the projectile momentum is dissipated before the model is applied.

Thomsen, J. M.↗

NASA NTRS1980

Extraterrestrial cause for the Cretaceous-Tertiary extinction

Direct physical evidence is presented for an unusual event at exactly the time of extinctions in the planktonic realm. Deep-sea limestones exposed in Italy, Denmark, and New Zealand indicate iridium increases of about 30, 160, and 20 times, respectively, above the background level at precisely the time of the Cretaceous-Tertiary extinctions, 65 million years ago. Reasons are given that this iridium is of extraterrestrial origin, but did not come from a nearby supernova. A hypothesis is set forth which accounts for the extinctions and the iridium observations. One prediction of this hypothesis is verified, that the chemical composition of the boundary clay, which is thought to come from the stratospheric dust, is markedly different from that of clay mixed with the chemically similar Cretaceous and Tertiary limestones.

Alvarez, L. W.↗

NASA NTRS1980

Microwave radiometer measurements of soil moisture content

A unique set of radiometer measurements is presented, recorded during a 1000-h day and night monitoring of irrigated fields from fully saturated to completely dry. Radiometer measurements were recorded at 2.8-cm (X-band) and 21.4-cm (L-band) wavelengths for a range of incident angles from nadir to 50 deg. Soil moisture and soil temperature profile measurements were recorded to a depth of 15 cm. The test site was located in east-central Texas on a clay soil (Miller clay). Three bare-surface plots were used, each having a distinctly different surface roughness. Vegetated plots were also measured. The data quantify the sensitivity of microwave radiometer measurements to soil moisture variations, the effect of surface roughness on the measurement, and the influence of surface vegetation.

Newton, R. W.↗

NASA NTRS1981

Mineralogical, optical, geochemical, and particle size properties of four sediment samples for optical physics research

X-ray diffraction and spectroscopy were used to investigate the mineralogical and chemical properties of the Calvert, Ball Old Mine, Ball Martin, and Jordan Sediments. The particle size distribution and index of refraction of each sample were determined. The samples are composed primarily of quartz, kaolinite, and illite. The clay minerals are most abundant in the finer particle size fractions. The chemical properties of the four samples are similar. The Calvert sample is most notably different in that it contains a relatively high amount of iron. The dominant particle size fraction in each sample is silt, with lesser amounts of clay and sand. The indices of refraction of the sediments are the same with the exception of the Calvert sample which has a slightly higher value.

Bice, K.↗