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Mineralogical and Chemical Characterization of Lunar Highland Soils: Insights into the Space Weathering of Soils on Airless Bodies

With reflectance spectroscopy, one is measuring only properties of the fine-grained regolith, most affected by space weathering. The Lunar Soil Characterization Consortium has undertaken the task of coordinated characterization of lunar soils, with respect to their mineralogical and chemical makeup. It is these lunar soils that are being used as "ground-truth" for all air30 less bodies. Modal abundances and chemistries of minerals and glasses in the finest size fractions (20-45, 10-20, and <10 microns) of four Apollo 14 and six Apollo 16 highland soils have been determined, as well as their bulk chemistry and IS/FeO values. Bi-directional reflectance measurements (0.3-2.6 microns) of all samples were performed in the RELAB. A significant fraction of nanophase Fe(sup 0) (np-Fe(sup 0)) appears to reside in agglutinitic glasses. However, as grain size of a soil decreases, the percentage of total iron present as np-Fe0 increases significantly, whereas the agglutinitic glass content rises only slightly; this is evidence for a large contribution to the IS/FeO values from the surface-correlated nanophase Fe(sup 0), particularly in the <10 micron size fraction. The compositions of the agglutinitic glasses in these fine fractions of the highland soils are different from the bulk-chemistry of that size; however, compositional trends of the glasses are not the same as those observed for mare soils. It is apparent that the glasses in the highland soils contain chemical components from outside their terrains. It is proposed that the Apollo 16 soils have been adulterated by the addition of impact-transported soil components from surrounding maria.

Taylor, Lawrence A.↗

Reflectance spectroscopy of ferric sulfate-bearing montmorillonites as Mars soil analog materials

Spectroscopic analyses have shown that smectites enhanced in the laboratory with additional ferric species exhibit important similarities to those of the soils on Mars. Ferrihydrite in these chemically treated smectites has features in the visible to near-infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. New samples have been prepared with sulfate as well, because S was found by Viking to be a major component in the surface material on Mars. A suite of ferrihydrite-bearing and ferric sulfate-bearing montmorillonites, prepared with variable Fe3+ and S concentrations and variable pH conditions, has been analyzed using reflectance spectroscopy in the visible and infrared regions, Mossbauer spectroscopy at room temperature and 4 K, differential thermal analysis, and X-ray diffraction. These analyses support the formation of ferrihydrite of variable crystallinity in the ferrihydrite-bearing montmorillonites and a combination of schwertmannite and ferrihydrite in the ferric sulfate-bearing montmorillonites. Small quantities of poorly crystalline or nanophase forms of other ferric materials may also be present in these samples. The chemical formation conditions of the ferrihydrite-bearing and ferric sulfate-bearing montmorillonites influence the character of the low temperature Mossbauer sextets and the visible reflectance spectra. An absorption minimum is observed at 0.88-0.89 micrometers in spectra of the ferric sulfate-bearing samples, and at 0.89-0.92 micrometers in spectra of the ferrihydrate-bearing montmorillonites. Mossbauer spectra of the ferric sulfate-bearing montmorillonites indicate variable concentrations of ferrihydrite and schwertmannite in the interlaminar spaces and along grain surfaces. Dehydration under reduced atmospheric pressure conditions induces a greater effect on the adsorbed and interlayer water in ferrihydrite-bearing montmorillonite than on the water in ferric sulfate-bearing montmorillonite. Reflectance spectra of ferric sulfate-bearing montmorillonite include a strong 3-micrometers band that is more resistant to dry atmospheric conditions than the 3-micrometers band in spectra of similarly prepared ferrihydrite-bearing montmorillonites.

NASA Discipline Exobiology↗

Understanding Martian Alteration Processes by Comparing In-Situ Chemical Measurements from Multiple Landing Sites

Characterizing the history of aqueous activity at the martian surface has been an objective of the Mars Exploration Rovers (MER) and the Mars Science Laboratory (MSL). Although the geologic context of the three landing sites are different, comparisons across the datasets can provide greater insight than using data from one mission alone. The Alpha Particle X-ray Spectrometer (APXS) is common to all three rovers (Spirit at Gusev crater, Opportunity at Meridiani Planum, and Curiosity at Gale crater) and provides a consistent basis for these comparisons. Soil and Dust: Fine grained basaltic soils and dust are remarkably uniform in chemical composition across multiple landing sites. These similarities in the concentrations of major, minor, and a few trace elements (Fig. 1) are indicative of planet-wide consistency in the composition of source materials for the soils. S and Cl vary by a factor of two in the soil and dust, but there is no clear association with any bulk cation (e.g., no correlation between S and total Ca, Mg, or Fe in soils). These volatile elements, however, are clearly associated with the nanophase-ferric iron component in the soil established by Mössbauer spectroscopy [1,2]. S and Cl likely originated as acidic species from volcanic out-gassing and subsequently coalesced on dust and sand grain surfaces, possibly with an affinity towards Fe3+ sites. Importantly, given the mobility of S and Cl in aqueous exposures, soil samples maintaining the typical molar S/Cl ratio of ~3.7:1 indicate minimal interactions with liquid water after the addition of S and Cl. In contrast to this well-established baseline, soil samples have been discovered at all three landing sites with atypical S/Cl ratios (e.g., subsurface soils), indicative of a more complex aqueous history.

Yen, A. S.↗

Thermal Emission Spectroscopy of Sulfates: Possible Hydrous Iron-Sulfate in the Soil at the MER-A Gusev Crater Landing Site

Sulfates are likely to be present on Mars as indicated by the sulfur abundances measured at the Viking and Pathfinder landing sites (approx. 5-10% by weight SO3) [1-3] and because of Mars strongly oxidizing environment. Telescopic observations of Mars tentatively identified weak sulfate bands in near infrared [4] and thermal infrared [5] data. The currently orbiting midinfrared instruments (TES, THEMIS) and the Mini-TES on the Mars Exploration Rover landers may enable a positive identification [6] and determination of the chemistry of the sulfates. Critically important to the identification of these minerals is the presence of their spectra in a spectral library. There exist approximately 370 sulfate-mineral species [7]. Sulfate minerals occur in volcanic, hydrothermal, evaporitic, and chemical-weathering environments.

Lane, Melissa D.↗

Evidence that the reactivity of the martian soil is due to superoxide ions

The Viking Landers were unable to detect evidence of life on Mars but, instead, found a chemically reactive soil capable of decomposing organic molecules. This reactivity was attributed to the presence of one or more as-yet-unidentified inorganic superoxides or peroxides in the martian soil. Using electron paramagnetic resonance spectroscopy, we show that superoxide radical ions (O2-) form directly on Mars-analog mineral surfaces exposed to ultraviolet radiation under a simulated martian atmosphere. These oxygen radicals can explain the reactive nature of the soil and the apparent absence of organic material at the martian surface.

long duration↗

Simulation of Viking biology experiments suggests smectites not palagonites, as martian soil analogues

An experimental comparison of palagonites and a smectite (montmorillonite) was performed in a simulation of the Viking Biology Labelled Release (LR) experiment in order to judge which mineral is a better Mars soil analog material (MarSAM). Samples of palagonite were obtained from cold weathering environments and volcanic soil, and the smectite was extracted from Wyoming Bentonite and converted to H or Fe types. Decomposition reaction kinetics were examined in the LR simulation, which on the Lander involved interaction of the martian soil with organic compounds. Reflectance spectroscopy indicated that smectites bearing Fe(III) in well-crystallized sites are not good MarSAMS. The palagonites did not cause the formate decomposition and C-14 emission detected in the LR, indicating that palagonites are also not good MarSAMS. Smectites, however, may be responsible for ion exchange, molecular adsorption, and catalysis in martian soil.

Banin, A.↗

Determination of natural and cosmic ray induced radionuclides in Apollo 17 lunar samples

Natural and cosmic ray induced radionuclides have been determined in 15 rocks and 7 soils from the Apollo 17 mission by nondestructive gamma-ray spectroscopy. The Th and K contents of these rocks and soils are shown to be linear functions of the U contents. Large amounts of Co-56, Sc-46, and Mn-54 were found in these samples due to the large proton-accelerating flares which occurred between August 2 and 6, 1972. The behavior of the Co-56 activity as a function of the Mn-54 activity seems to be the result of variation in surface to volume ratios among the samples and exposure angle. It is not necessary to invoke an asymetric solar flare flux to explain this behavior.

Keith, J. E.↗

Colloquium on Water in Planetary Regoliths, Hanover, N.H., October 5-7, 1976, Proceedings

The papers abstracted in this volume deal with the occurrence, detection, and measurement of water on planetary bodies in the solar system; relevant aspects of the terrestrial water balance; the most probable status of water on other planetary bodies; and the methods of water detection and measurement available for consideration in designing planetary exploration missions. Topics include the water inventory for earth, high-energy protons as an early source of regolith water, the evolution of water on Mars, the chemical evolution of the Martian atmosphere by surface weathering, some geochemical aspects of excess volatiles on Mars, fluvial erosion on Mars, water in the outer solar system, and the stability of water on the Galilean satellites. Other papers discuss gamma-ray attenuation methods for determining the water content of soil, Viking biology-experiment results relevant to water on Mars, IR detection of water ice on satellite surfaces during the Mariner Jupiter/Saturn mission, electrical sounding of the lunar regolith, the detection of water on the moon and Mars by orbital gamma-ray spectroscopy, and the Viking Martian soil-water analyzer.

Bowen, S.L.↗

Observation of iron-rich coating on lunar grains and a relation to low albedo

The outermost few atomic layers of lunar soil samples were studied by Auger spectroscopy and were found to contain in each case two to three times more iron than the mean bulk composition of the sample. The amount of excess iron is found to be closely correlated with the optical albedo in the manner that would be theoretically expected if the iron provided absorption centers. Crushed lunar rocks of similar mean composition, but lacking the extra iron coating of the soil grains, have a much higher albedo than most lunar soils sampled or observed on the lunar surface.

Gold, T.↗

Effects of material mixing on planetary gamma ray spectroscopy

The effect of mixing of rocks and soil on the gamma-ray signal emitted by Martian surface was investigated with special consideration given to the effect of the geometry of mixing. It is shown that, under certain circumstances, this scale can have a significant effect on the gamma-ray spectrum observed. The techniques that can be used to address this problem are discussed, showing that, using these techniques, rock compositions can be inferred from the signal produced by a rock-soil mixtures of unknown rock concentration and mixing geometry.

Squyres, Steven W.↗

Use of near infrared correlation spectroscopy for quantitation of surface iron, absorbed water and stored electronic energy in a suite of Mars soil analog materials

A number of questions concerning the surface mineralogy and the history of water on Mars remain unresolved using the Viking analyses and Earth-based telescopic data. Identification and quantitation of iron-bearing clays on Mars would elucidate these outstanding issues. Near infrared correlation analysis, a method typically applied to qualitative and quantitative analysis of individual constituents of multicomponent mixtures, is adapted here to selection of distinctive features of a small, highly homologous series of Fe/Ca-exchanged montmorillonites and several kalinites. Independently determined measures of surface iron, relative humidity and stored electronic energy were used as constituent data for linear regression of the constituent vs. reflectance data throughout the spectral region 0.68 to 2.5 micrometers. High correlations were found in appropriate regions for all three constituents, though that with stored energy is still considered tenuous. Quantitation was improved using 1st and 2nd derivative spectra. High resolution data over a broad spectral range would be required to quantitatively identify iron-bearing clays by remotely sensed reflectance.

Coyne, Lelia M.↗

The search for the cause of the low albedo of the moon

The effects of different weathering processes on the albedo of the lunar surface cover is discussed. The surface chemical composition of numerous lunar soil and pulverized rock samples was determined by auger electron spectroscopy. The optical albedo of these samples was also measured. The chemical concentration of iron and titanium is greater on the surface of soil samples than it is on the surface of crushed rock samples with similar bulk composition, whereas the albedo of soil samples is lower than that of the crushed rock samples. A correlation is presented between the surface iron + titanium content and the albedo. Results of solar wind simulation experiments show that irradiation of crushed lunar rock samples with a small dose (corresponding to 3000 years of solar wind) of 2-keV energy protons changed the surface chemistry of the rock to that of the soil. A much larger dose of protons (corresponding to 30,000 years of solar wind) was needed to darken crushed rock to the albedo of the soil of similar bulk chemical composition. The mechanism of darkening by solar wind is discussed, and its effectiveness is compared to that of other darkening processes.

Gold, T.↗

MSL Chemistry and Mineralogy X-Ray Diffraction X-Ray Fluorescence (CheMin) Instrument

This paper provides an overview of the Mars Science Laboratory (MSL) Chemistry and Mineralogy Xray Diffraction (XRD), X-ray Fluorescence (XRF) (CheMin) Instrument, an element of the landed Curiosity rover payload, which landed on Mars in August of 2012. The scientific goal of the MSL mission is to explore and quantitatively assess regions in Gale Crater as a potential habitat for life - past or present. The CheMin instrument will receive Martian rock and soil samples from the MSL Sample Acquisition/Sample Processing and Handling (SA/SPaH) system, and process it utilizing X-Ray spectroscopy methods to determine mineral composition. The Chemin instrument will analyze Martian soil and rocks to enable scientists to investigate geophysical processes occurring on Mars. The CheMin science objectives and proposed surface operations are described along with the CheMin hardware with an emphasis on the system engineering challenges associated with developing such a complex instrument.

sample chemistry↗

Detection of Soluble and Fixed NH4+ in Clay Minerals by DTA and IR Reflectance Spectroscopy : A Potential Tool for Planetary Surface Exploration

Nitrogen is an essential element for life. It is the only element among the six major biogenic elements, C, O, S, O, P, H, whose presence in the Martian soil has not been positively and directly established. We describe here a study assessing the ability to detect NH4 in soils by two methods: differential thermal analysis (DTA) and infrared (IR) reflectance spectroscopy. Four standard clay minerals (kaolinite, montmorillonite, illite and attapulgite) and an altered tephra sample from Mauna Kea were treated with NH4 in this study. Samples of the NH4-treated and leached clays were analyzed by DTA and infrared (IR) reflectance spectroscopy to quantify the delectability of soluble and sorbed/fixed NH4. An exotherm at 270-280 C was clearly detected in the DTA curves of NH4-treated (non-leached) samples. This feature is assigned to the thermal decomposition reaction of NH4. Spectral bands observed at 1.56, 2.05, 2.12, 3.06, 3.3, 3.5, 5.7 and 7.0 microns in the reflectance spectra of NH4-treated and leached samples are assigned to the sorbed/fixed ammonium in the clays. The montmorillonite has shown the most intense absorbance due to fixed ammonium among the leached samples in this study, as a result of its high cation sorption capacity. It is concluded that the presence of sorbed or fixed NH4 in clays may be detected by infrared (IR) reflectance or emission spectroscopy. Distinction between soluble and sorbed NH4 may be achieved through the presence or absence of several spectral features assigned to the sorbed NH4 moietyi and, specifically, by use of the 4.2 micrometer feature assigned to solution NH4. Thermal analyses furnish supporting evidence of ammonia in our study through detection of N released at temperatures of 270-330 C. Based on these results it is estimated that IR spectra measured from a rover should be able to detect ammonia if present above 20 mg NH4/g sample in the surface layers. Orbital IR spectra and thermal analyses measured on a rover may be able to detect ammonia in soils as well but at higher abundances. The spectral features at 3.06 and 7.0 microns due to bound NH4 in clays and altered Hawaiian tephra appear to be the most promising for detection by orbital spectrometers. If N species are present on Mars the sedimentary deposits may be the best regions to look for them.

Janice, Bishop↗

Confirmation of Soluble Sulfate at the Phoenix Landing Site: Implications for Martian Geochemistry and Habitability

Over the past several decades, elemental sulfur in martian soils and rocks has been detected by a number of missions using X-ray spectroscopy [1-3]. Optical spectroscopy has also provided evidence for widespread sulfates on Mars [4,5]. The ubiquitous presence of sulfur in soils has been interpreted as a widely distributed sulfate mineralogy [6]. However, direct confirmation as to the identity and solubility of the sulfur species in martian soil has never been obtained. One goal of the Wet Chemistry Laboratory (WCL) [7] on board the 2007 Phoenix Mars Lander [8] was to determine soluble sulfate in the martian soil. The WCL received three primary samples. Each sample was added to 25 mL of leaching solution and analysed for solvated ionic species, pH, and conductivity [9,10]. The analysis also showed a discrepancy between charge balance, ionic strength, and conductivity, suggesting unidentified anionic species.

Kounaves, S. P.↗