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Morris, Richard V.

Publications and source records attributed to Morris, Richard V..

At least 37 records · Page 2

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise approx 20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000 C and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures < 500 C, and an evolution peak at higher temperatures near approx 750 C. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the approx 20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples

McAdam, Amy↗

Characterizing the Phyllosilicates and Amorphous Phases Found by MSL Using Laboratory XRD and EGA Measurements of Natural and Synthetic Materials

The Curiosity Rover landed on the Peace Vallis alluvial fan in Gale crater on August 5, 2012. A primary mission science objective is to search for past habitable environments, and, in particular, to assess the role of past water. Identifying the minerals and mineraloids that result from aqueous alteration at Gale crater is essential for understanding past aqueous processes at the MSL landing site and hence for interpreting the site's potential habitability. X-ray diffraction (XRD) data from the CheMin instrument and evolved gas analyses (EGA) from the SAM instrument have helped the MSL science team identify phases that resulted from aqueous processes: phyllosilicates and amorphous phases were measure in two drill samples (John Klein and Cumberland) obtained from the Sheepbed Member, Yellowknife Bay Fm., which is believed to represent a fluvial-lacustrine environment. A third set of analyses was obtained from scoop samples from the Rocknest sand shadow. Chemical data from the APXS instrument have helped constrain the chemical compositions of these secondary phases and suggest that the phyllosilicate component is Mg-enriched and the amorphous component is Fe-enriched, relatively Si-poor, and S- and H-bearing. To refine the phyllosilicate and amorphous components in the samples measured by MSL, we measured XRD and EGA data for a variety of relevant natural terrestrial phyllosilicates and synthetic mineraloids in laboratory testbeds of the CheMin and SAM instruments. Specifically, Mg-saturated smectites and vermiculites were measured with XRD at low relative humidity to understand the behavior of the 001 reflections under Mars-like conditions. Our laboratory XRD measurements suggest that interlayer cation composition affects the hydration state of swelling clays at low RH and, thus, the 001 peak positions. XRD patterns of synthetic amorphous materials, including allophane, ferrihydrite, and hisingerite were used in full-pattern fitting (FULLPAT) models to help determine the types and abundances of amorphous phases in the martian rocks and sand shadow. These models suggest that the rocks and sand shadow are composed of approx 30% amorphous phases. Sulfate-adsorbed allophane and ferrihydrite were measured by EGA to further understand the speciation of the sulfur present in the amorphous component. These data indicate that sulfate adsorbed onto the surfaces of amorphous phases could explain a portion of the SO2 evolution in the Rocknest SAM data. The additional constraints placed on the mineralogy and chemistry of the aqueous alteration phases through our laboratory measurements can help us better understand the nature of the fluids that affected the different samples and devise a history of aqueous alteration for the Sheepbed Member of the Yellowknife Bay Fm. at Gale crater.

Rampe, Elizabeth B.↗

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

Morris, Richard V.↗

Terrestrial Analogs for Clay Minerals at Yellowknife Bay, Gale Crater, Mars

Sediments of the Sheepbed unit, Gale Crater, were analyzed by the CheMin X-ray diffraction instrument on the Curiosity Rover. The sediments consist of typical basalt minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe oxide/hydroxides, Fesulfides, amorphous material, and a phyllosilicate. The phyllosilicate has a broad 001 peak at approx 1.0 nm, consistent with a poorly ordered smectite. However, in the absence of diagnostic tests possible on Earth, its identity is not clear. The position of the 06L diffraction band is generally used to distinguish dioctahedral from trioctahedral smectite, but it is beyond CheMin's range of 2 Theta. The measured position of the 02L diffraction band (approx 22.5deg 2 Theta by CheMin), implies that the smectite is trioctahedral. The exact position and shape of the 02L band is determined by the cations in the 'M' sites of the smectite; to constrain those cations, we sought analogs among terrestrial smectites, emphasizing those developed from basaltic precursors. A potential analog for the Sheepbed smectite is 'griffithite,' a variety of trioctahedral smectite in altered basalt of the Topanga formation, Griffith Park, Los Angeles. 'Griffithite' has an 02L diffraction band that is close in position and shape to that of the Sheepbed smectite, although 'griffithite' has a very sharp 001 peak, indicating a high degree of layer ordering not seen in the Sheepbed smectite. A typical chemical formula for 'griffithite,' determined by electron microprobe, is (Ca0.59 Na0.03) (Mg4.28 Fe1.83) (Si6.64 Al1.36) O20 (OH)4, normalized to Si+Al=8. This formula is consistent with a fully trioctahedral Fe-Mg smectite with Ca and Na as interlayer cations. In the Topanga basalt, four types of 'griffithite' are present: fine-grained, filling cracks and vesicles; coarse-grained, filling vesicles; coarse-grained, replacing olivine phenocrysts; and coarse-grained, replacing glassy mesostasis. The fine-grained 'griffithite' formed first, and the last three varieties may be contemporaneous. One sample shows agate (alpha- quartz) that was precipitated between the episodes of deposition of the fine-grained and coarse-grained 'griffithite.' 'Griffithite' is not unique as a possible terrestrial analog - some clay minerals from the Doushantou formation, China, have similar 02L diffraction bands, and many basalts contain smectites in vesicles and as replacements after olivine. Similar trioctahedral smectites occur also in the nakhlite martian meteorites - as veinlets and replacements of olivine. By understanding the formation of these terrestrial clays, we hope to constrain the nature and mechanism of formation of the Sheepbed clay mineral.

Treiman, Allan H↗

Isotopic and Geochemical Investigation of Two Distinct Mars Analog Environments Using Evolved Gas Techniques in Svalbard, Norway

The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two distinct geologic settings on Svalbard, using methodologies and techniques to be deployed on Mars Science Laboratory (MSL). AMASErelated research comprises both analyses conducted during the expedition and further analyses of collected samples using laboratory facilities at a variety of institutions. The Sample Analysis at Mars (SAM) instrument suite on MSL includes pyrolysis ovens, a gas-processing manifold, a quadrupole mass spectrometer (QMS), several gas chromatography columns, and a Tunable Laser Spectrometer (TLS). An integral part of SAM development is the deployment of SAM-like instrumentation in the field. During AMASE 2010, two parts of SAM participated as stand-alone instruments. A Hiden Evolved Gas Analysis- Mass Spectrometer (EGA-QMS) system represented the EGA-QMS component of SAM, and a Picarro Cavity Ring Down Spectrometer (EGA-CRDS), represented the EGA-TLS component of SAM. A field analog of CheMin, the XRD/XRF on MSL, was also deployed as part of this field campaign. Carbon isotopic measurements of CO2 evolved during thermal decomposition of carbonates were used together with EGA-QMS geochemical data, mineral composition information and contextual observations made during sample collection to distinguish carbonates formation associated with chemosynthetic activity at a fossil methane seep from abiotic processes forming carbonates associated with subglacial basaltic eruptions. Carbon and oxygen isotopes of the basalt-hosted carbonates suggest cryogenic carbonate formation, though more research is necessary to clarify the history of these rocks.

Svalbard↗

Definitive Mineralogy from the Mars Science Laboratory Chemin Instrument

The Mars Science Laboratory (MSL) rover will land in Gale Crater on Mars in August 2012. The planned landing site is an alluvial fan near the base of the crater's central mound. Orbital remote sensing of this 5 km high mound indicates the presence of hydrated sulfates, interstratified with smectite and hematite-bearing layers. Minerals formed in an aqueous environment are of particular interest given that water is a fundamental ingredient of living systems and that MSL's prime science objective is to investigate martian habitability.

Yen, A. S.↗

Moon and Mars Analog Mission Activities for Mauna Kea 2012

Rover-based 2012 Moon and Mars Analog Mission Activities (MMAMA) scientific investigations were recently completed at Mauna Kea, Hawaii. Scientific investigations, scientific input, and science operations constraints were tested in the context of an existing project and protocols for the field activities designed to help NASA achieve the Vision for Space Exploration. Initial science operations were planned based on a model similar to the operations control of the Mars Exploration Rovers (MER). However, evolution of the operations process occurred as the analog mission progressed. We report here on the preliminary sensor data results, an applicable methodology for developing an optimum science input based on productive engineering and science trades discussions and the science operations approach for an investigation into the valley on the upper slopes of Mauna Kea identified as "Apollo Valley".

Graham, Lee D.↗

Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant to the dry N2 treatment for saponite and the montmorillionites, but the nontronites had additional structural OH after treatment. Upon exposure to dry N2, the VNIR spectra also acquired a red slope with decreasing albedo between approximately 0.4 and approximately 2.0 micrometers. The magnitude of the effects covaries with exposure time to dry N2 and heating temperature. Upon re-exposure to lab air, the slope and albedo do not completely recover to pre-exposure values. MB data show that these effects do not result from partial reduction of ferric to ferrous iron, and TG data show they do not result from loss of structural OH. Possible explanations include formation of small clusters of (superparamagnetic) ferric oxide and reduced smectite crystallinity. The difference in spectral properties between spectra acquired in humid lab air and under dry conditions are consequential for interpretation of CRISM and OMEGA spectra. For example, nontronite by itself and not nontronite plus ferrihydrite can account for the red spectral slope in martian spectra where nontronite is indicated by the Fe-OH spectral features.

Morris, Richard V.↗

Moessbauer Spectroscopy of Martian and Sverrefjell Carbonates

Mars, in its putative "warmer, wetter: early history, could have had a CO2 atmosphere much denser than its current value of <10 mbar. The question of where all this early CO2 has gone has long been debated. Now, several instruments on Mars Exploration Rover (MER) Spirit, including its Moessbauer spectrometer MIMOS II, have identified Mg-Fe carbonate in rock outcrops at Comanche Spur in the Columbia Hills of Gusev Crater. With this finding, carbonate cements in volcanic breccia collected on Sverrefjell Volcano on Spitzbergen Island in the Svalbard Archipelago (Norway) during the AMASE project are mineralogical and possible process analogues of the newly discovered martian carbonate. We report further analyses of Mossbauer spectra from Comanche Spur and discuss their relationship to Mossbauer data acquired on Sverrefjell carbonates. The spectra were velocity calibrated with MERView and fit using MERFit. Instead of the "average temperature" Comanche spectrum (data from all temperature windows summed), we refit the Comanche data for QS within each temperature window, modeling as doublets for Fe2+(carbonate), Fe2+(olivine), and Fe3+(npOx). The temperature dependences of QS for the Comanche carbonate and for a low-Ca carbonate from Chocolate Pots in Yellowstone National Park (YNP) are shown; they are the same within error. For Comanche carbonate summed over 210-270 K, (CS, QS) = (1.23, 1.95) mm/s. The value of QS for Sverrefjell carbonate at 295 K, (CS, QS) = (1.25, 1.87) mm/s, is also plotted, and the plot shows that the QS for the Sverrefjell carbonate agrees within error with the Comanche data extrapolated to 295 K. This agreement is additional evidence that the Sverrefjell carbonates are Mossbauer analogues for the Comanche carbonates, and that both carbonates might have precipitated from solutions that became carbonate rich by passing through buried carbonate deposits.

Agresti, David G.↗

A Terrestrial Analogue from Spitsbergen (Svalbard, Norway) for the Comanche Carbonate at Gusev Crater, Mars

Carbonate occurs at the Comanche outcrops in Gusev Crater on the basis of analyses made by the Mars Exploration Rover Spirit [1]. Taken together, mineralogical data from Spirit's Moessbauer (MB) and Mini-TES spectrometer and chemical data from the APXS spectrometer show that Comanche carbonate has an Mg-Fe-rich bulk chemical composition, is present at high concentrations, and is distributed throughout the outcrop and not just at the MB and APXS analysis location. The granular outcrop texture and the observation that it appears to be resistant to weathering compared with surrounding material [1] imply that the carbonate may be present as a cement. A hydrothermal origin for the Comanche carbonate was inferred by analogy with laboratory experiments and with a carbonate occurrence within the Bockfjord volcanic complex on the island Spitsbergen (Svalbard, Norway) [1]. The laboratory carbonates, synthesized by precipitation from hydrothermal solutions, have (MB) parameters and average bulk chemical compositions that are characteristic of Comanche carbonate. The connection to Comanche carbonate is only through chemical data for certain occurrences of Spitsbergen carbonates. In fact, the common average bulk chemical composition for these Spitsbergen carbonates, the synthetic carbonates, the Comanche carbonate, and also the carbonate globules found in martian meteorite ALH84001 is a chemical constraint consistent with a hydrothermal formation process for all the carbonates [e.g., 1-3]. We develop here a link between MB data for the Comanche carbonate from MER and MB data for certain Spitsbergen carbonate occurrences from laboratory measurements. We also obtained visible and near- IR spectra on Spitsbergen carbonates for comparison with martian carbonate detections made on the basis of CRISM spectral data, e.g., in Nili Fossae [4].

Morris, Richard V.↗

Poorly Crystalline, Iron-Bearing Aluminosilicates and Their Importance on Mars

Martian rocks and sediments contain weathering products including evaporite salts and clay minerals that only form as a result of interaction between rocks and water [1-6]. These weathering products are key to studying the history of water on Mars because their type, abundance and location provide clues to past conditions on the surface of the planet, as well as to the possible location of present-day reservoirs of water. Weathering of terrestrial volcanic rocks similar to those on Mars produces nano-sized, variably hydrated aluminosilicate and iron oxide minerals [7-10] including allophane, imogolite, halloysite, hisingerite, and ferrihydrite. The nanoaluminosilicates can contain isomorphically substituted Fe, which affects their spectral and physical properties. Detection and quantification of such minerals in natural environments on earth is difficult due to their variable chemical composition and lack of long-range crystalline order [9, 11, 12]. Despite the difficulty in characterizing these materials, they are common on Earth, and data from orbital remote sensing and rover-based instruments suggest that they are also present on Mars [9, 10, 13-17]. Their accurate detection and quantification require a better understanding of how composition affects their spectral properties. We present here the results of XAFS spectroscopy; these results will be corroborated with planned Mossbauer and reflectance spectroscopy.

Baker, L. L.↗

Discovery of Carbonate-Rich Outcrops in the Gusev Crater Columbia Hills by the MER Rover Spirit

The chemical composition, global abundance, distribution, and formation pathways of carbonates are central to understanding aqueous processes, climate, and habitability of early Mars. The Mars Exploration Rover (MER) Spirit analyzed a series of olivine-rich outcrops while descending from the summit region of Husband Hill into the Inner Basin of the Columbia Hills of Gusev Crater to the eastern edge of the El Dorado ripple field in late 2005. Reanalysis of Spirit s mineralogical data from the Moessbauer Spectrometer (MB) and the Miniature Thermal Emission Spectrometer (Mini-TES) and chemical data from the Alpha Particle X-Ray Spectrometer (APXS) in 2010, coupled with new laboratory data for carbonate-bearing samples, lead to identification of carbonate in one of the outcrops (Comanche) [Morris, R.V., et al., Science, 329, 421-424]. The carbonate is rich in magnesium and iron (Mc62Sd25Cc11Rh2, assuming all Ca and Mn is associated with the carbonate) and is a major component of the Comanche outcrops (16 to 34 wt.%). The mineralogical, chemical, and abundance data are constrained in multiple, mutually consistent ways by the MER analyses. For example, a low-Ca carbonate is required by the MB and APXS data and is consistent with Mini-TES data. Three spectral features attributable to fundamental infrared vibrational modes of low-Ca carbonate are present in the Mini-TES spectra of Comanche outcrops. The average composition of Comanche carbonate approximates the average composition of the carbonate globules in Martian meteorite ALH 84001. Analogy with ALH 84001, terrestrial, and synthetic carbonate globules suggests that Comanche carbonate precipitated from aqueous solutions under hydrothermal conditions at near neutral pH in association with volcanic activity during the Noachian era. Comanche outcrop morphology suggests they are remnants of a larger carbonate-bearing formation that evolved in ultramafic rock and then preferentially eroded by a combination of aeolian abrasion and chemical decomposition by exposure to acid-sulfate vapors/solutions. The high carbonate concentration in the Comanche outcrops supports climate models involving a CO2 greenhouse gas on a wet and warm early Mars and subsequent sequestering of at least part of that atmosphere in carbonate minerals.

Morris, Richard V.↗

Mineralogy of SNC Meteorite EET79001 by Simultaneous Fitting of Moessbauer Backscatter Spectra

We have acquired M ssbauer spectra for SNC meteorite EET79001 with a MIMOS II backscatter M ssbauer spectrometer [1] similar to those now operating on Mars as part of the Mars Exploration Rover (MER) missions. We are working to compare the Fe mineralogical composition of martian meteorites with in-situ measurements on Mars. Our samples were hand picked from the >1 mm size fraction of saw fines on the basis of lithology, color, and grain size (Table 1). The chips were individually analyzed at approx.300K by placing them on a piece of plastic that was in turn supported by the contact ring of the instrument (oriented vertically). Tungsten foil was used to mask certain areas from analysis. As shown in Figure 1, a variety of spectra was obtained, each resulting from different relative contributions of the Fe-bearing minerals present in the sample. Because the nine samples are reasonably mixtures of the same Fe-bearing phases in variable proportions, the nine spectra were fit simultaneously (simfit) with a common model, adjusting parameters to a single minimum chi-squared convergence criterion [2]. The starting point for the fitting model and values of hyperfine parameters was the work of Solberg and Burns [3], who identified olivine, pyroxene, and ferrous glass as major, and ilmenite and a ferric phase as minor (<5%), Fe-bearing phases in EET79001.

Morris, Richard V.↗

Partial Least Squares and Neural Networks for Quantitative Calibration of Laser-induced Breakdown Spectroscopy (LIBs) of Geologic Samples

The ChemCam instrument [1] on the Mars Science Laboratory (MSL) rover will be used to obtain the chemical composition of surface targets within 7 m of the rover using Laser Induced Breakdown Spectroscopy (LIBS). ChemCam analyzes atomic emission spectra (240-800 nm) from a plasma created by a pulsed Nd:KGW 1067 nm laser. The LIBS spectra can be used in a semiquantitative way to rapidly classify targets (e.g., basalt, andesite, carbonate, sulfate, etc.) and in a quantitative way to estimate their major and minor element chemical compositions. Quantitative chemical analysis from LIBS spectra is complicated by a number of factors, including chemical matrix effects [2]. Recent work has shown promising results using multivariate techniques such as partial least squares (PLS) regression and artificial neural networks (ANN) to predict elemental abundances in samples [e.g. 2-6]. To develop, refine, and evaluate analysis schemes for LIBS spectra of geologic materials, we collected spectra of a diverse set of well-characterized natural geologic samples and are comparing the predictive abilities of PLS, cascade correlation ANN (CC-ANN) and multilayer perceptron ANN (MLP-ANN) analysis procedures.

Anderson, R. B.↗

Hematite at Meridiani Planum, Mars, Investigated by Simultaneous Fitting of MER Mossbauer Spectra

The Mars Exploration Rover Opportunity encountered sedimentary outcrop rocks at its landing site. Spherules with diameters in the millimeter range were found to weather from the outcrop rocks. With Opportunity s miniaturised M ssbauer spectrometer MIMOS II, hematite was detected in spherules and in the outcrop matrix [1,2]. Figure 1 shows the target Berry Bowl, where brushed outcrop and an accumulation of spherules could be investigated on sols 46 and 48 of Opportunity s mission. Hematite undergoes a transition from a weakly ferromagnetic above to an antiferromagnetic state below the Morin temperature (T(sub M) approx.265 K for chemically pure, crystalline hematite). The magnetic hyperfine splitting (B(sub hf)) shows a general decrease with increasing temperature and a drop of approx.0.8 T at T(sub M). The quadrupole splitting ((Delta)EQ) changes its sign at T(sub M), with negative values above and positive values below the transition. Crystallinity and particle size influence the magnitude and temperature dependence of the magnetic splitting and the quadrupole splitting [3].

Fleischer, I.↗

Evidence for Interlayer Collapse of Nontronite on Mars from Laboratory Visible and Near-IR Reflective Spectra

Dioctahedral smectites (e.g., nontronite and montmorillionite) are interpreted to occupy the optical surface of Mars at a number of locations on the basis of spectral features derived from interlayer H2O and MOH (M=Fe(3+)2, Fe(3+)Al, Al2, etc.) as observed by orbiting MRO-CRISM and MEx-OMEGA hyperspectral imaging spectrometers. At wavelengths shorter than approximately 2.7 micrometers, the strongest bands from interlayer H2O occur at approximately 1.4 and 1.9 micrometers from 2v1 and v1+v2, respectively, where v1 and v2 are the fundamental stretching and bending vibrations of the H2O molecule. Smectite MOH vibrations occur near 1.4 micrometers (stretching overtone) and in the region between 2.1 and 2.7 micrometers (stretching + bending combination). Because interlayer H2O can exchange with the martian environment, a number of studies have examined the strength of the interlayer H2O spectral features under Mars-like environmental conditions. The relationship between spectral properties and the underlying crystal structure of the smectites was not determined, and the extent of interlayer H2O removal was not established. We report combined visible and near-IR (VNIR), Mossbauer (MB), and powder X-ray diffraction (XRD) data for samples of the Fe-bearing smectite nontronite where the interlayer was collapsed by complete removal of interlayer H2O.

Morris, Richard V.↗

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.↗

Hematite-Rich Fracture Fill at Meridiani Planum, Mars: Implications for Fluid Chemistry

The Mars Exploration Rover Opportunity has been operating at the surface of Mars for over 2100 sols and has driven a distance of approximately 20 km. Throughout the traverse, outcrop rocks with margins and fracture fill resistant to erosion have been imaged and analyzed in detail by the Moessbauer (MB) spectrometer and the Alpha Particle X-ray Spectrometer (APXS). A recent APXS analysis of an outcrop block excavated by a young impact crater shows a coating with the highest concentration of iron measured by either rover, not including the iron-nickel meteorites. Texturally, this sample (referred to as "Chocolate Hills -Aloya") appears as a cemented collection of partially fragmented \blueberries." With the exception of an elevated sulfur content, the elemental chemistry of this particular sample is entirely consistent with other analyses of hematite spherules at Merdiani Planum. As a result, it is difficult to determine whether this coating, which may have been filling a fracture in outcrop rocks prior to disruption by the impact, was simply an agglomeration of spherules or a result of a more complicated aqueous process. In contrast, a number of other fracture-filling exposures and erosion-resistant rinds have been analyzed by the APXS and MB instruments showing significant concentrations of iron in the form of hematite without the texture of spherule fragments. In one of these samples, a broken piece of fracture fill within Victoria crater referred to as "Dorsal," showed over 50% of the iron in hematite, the highest Mn concentration of any sample measured by the rovers, and elevated levels of Cl and Br. While the Fe:Mn ratio of the Dorsal analyses are comparable to that of Gusev and Meridiani basalts, it is clear that chemistry of this sample cannot be completely explained by a simple mixing of outcrop and blueberry compositions

Yen, Albert↗