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Clegg, S. M.

Publications and source records attributed to Clegg, S. M..

Manganese-Rich Sandstones as an Indicator of Ancient Oxic Lake Water Conditions in Gale Crater, Mars

Manganese has been observed on Mars by the NASA Curiosity rover in a variety of contexts and is an important indicator of redox processes in hydrologic systems on Earth. Within the Murray formation, an ancient primarily fine-grained lacustrine sedimentary deposit in Gale crater, Mars, have observed up to 45× enrichment in manganese and up to 1.5× enrichment in iron within coarser grained bedrock targets compared to the mean Murray sediment composition. This enrichment in manganese coincides with the transition between two stratigraphic units within the Murray: Sutton Island, interpreted as a lake margin environment, and Blunts Point, interpreted as a lake environment. On Earth, lacustrine environments are common locations of manganese precipitation due to highly oxidizing conditions in the lakes. Here, we explore three mechanisms for ferromanganese oxide precipitation at this location: authigenic precipitation from lake water along a lake shore, authigenic precipitation from reduced groundwater discharging through porous sands along a lake shore, and early diagenetic precipitation from groundwater through porous sands. All three scenarios require highly oxidizing conditions and we discuss oxidants that may be responsible for the oxidation and precipitation of manganese oxides. This work has important implications for the habitability of Mars to microbes that could have used Mn redox reactions, owing to its multiple redox states, as an energy source for metabolism.

58 GEOSCIENCES↗

Apatites in Gale Crater

ChemCam is an active remote sensing instrument suite that has operated successfully on MSL since landing Aug. 6th, 2012. It uses laser pulses to remove dust and to analyze rocks up to 7 m away. Laser-induced breakdown spectroscopy (LIBS) obtains emission spectra of materials ablated from the samples in electronically excited states. The intensities of the emission lines scale with the abundances of the related element. ChemCam is sensitive to most major rock-forming elements as well as to a set of minor and trace elements such as F, Cl, Li, P, Sr, Ba, and Rb. The measured chemical composition can then be used to infer the mineralogical composition of the ablated material. Here, we report a summary of inferred apatite detections along the MSL traverse at Gale Crater. We present the geologic settings of these findings and derive some interpretations about the formation conditions of apatite in time and space.

Forni, O.↗

Oxidation Of Manganese At Kimberley, Gale Crater: More Free Oxygen In Mars' Past?

High Mn concentrations provide unique indicators of water-rich environments and their redox state. Very high-potential oxidants are required to oxidize Mn to insoluble, high-valence oxides that can precipitate and concentrate Mn in rocks and sediments; these redox potentials are much higher than those needed to oxidize Fe or S. Consequently, Mn-rich rocks on Earth closely track the rise of atmospheric oxygen. Given the association between Mn-rich rocks and the redox state of surface environments, observations of anomalous Mn enrichments on Mars raise similar questions about redox history, solubility and aqueous transport, and availability as a metabolic substrate. Our observations suggest that at least some of the high Mn present in Gale crater occurs in the form of Mn-oxides filling veins that crosscut sand-stones, requiring post-depositional precipitation as highly oxidizing fluids moved through the fractured strata after their deposition and lithification.

Lanza, N. L.↗

Fluorine and Lithium at the Kimberley Outcrop, Gale Crater

ChemCam is an active remote sensing instrument which has operated successfully on MSL since landing in August, 2012. Its laser pulses remove dust and to profile through weathering coatings of rocks up to 7 m away. Laser-induced breakdown spectroscopy (LIBS) produces emission spectra of materials ablated from the samples in electronically excited states. As the plasma cools, elements can recombine and molecular emission lines are observed. Recent experiments have shown that some of these molecular emissions can be much brighter than the associated atomic lines, especially when halo-gens and rare earth elements are present. We observed these molecular emissions in some of the ChemCam spectra and report the first detection of chlorine and fluorine with ChemCam. It is also the first time ever that fluorine has been detected on the surface of Mars. Among all the F-bearing observations, one third are observed in the Kimberley outcrop. We will dis-cuss the potential mineralogies related to these observations as well as the related elemental correlations and propose interpretations.

Forni, O.↗

Calcium Sulfate Characterized by Chemcam/Curiousity at Gale Crater, Mars

Onboard the Mars Science Laboratory (MSL) Curiosity rover, the ChemCam instrument consists of : (1) a Laser-Induced Breakdown Spectrometer (LIBS) for elemental analysis of the targets and (2) a Remote Micro Imager (RMI), for the imaging context of laser analysis. Within the Gale crater, Curiosity traveled from Bradbury Landing through the Rocknest region and into Yellowknife Bay (YB). In the latter, abundant light-toned fracture-fill material occur. ChemCam analysis demonstrates that those fracture fills consist of calcium sulfates.[

Nachon, M.↗

Update on Development of the Potassium-Argon Laser Experiment (KArLE) Instrument for In Situ Geochronology

Absolute dating of planetary samples is an essential tool to establish the chronology of geological events, including crystallization history, magmatic evolution, and alteration. We are addressing this challenge by developing the Potassium (K) -- Argon Laser Experiment (KArLE), building on previous work to develop a K-Ar in situ instrument. KArLE ablates a rock sample, determines the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measures the liberated Ar using quadrupole mass spectrometry (QMS), and relates the two by the volume of the ablated pit using laser confocal microscopy (LCM). Our goal is for the KArLE instrument to be capable of determining the age of several kinds of planetary samples to address a wide range of geochronolgy problems in planetary science.

Cohen, Barbara A.↗

Development of the Potassium-Argon Laser Experiment (KArLE) Instrument for In Situ Geochronology

Absolute dating of planetary samples is an essential tool to establish the chronology of geological events, including crystallization history, magmatic evolution, and alteration. Traditionally, geochronology has only been accomplishable on samples from dedicated sample return missions or meteorites. The capability for in situ geochronology is highly desired, because it will allow one-way planetary missions to perform dating of large numbers of samples. The success of an in situ geochronology package will not only yield data on absolute ages, but can also complement sample return missions by identifying the most interesting rocks to cache and/or return to Earth. In situ dating instruments have been proposed, but none have yet reached TRL 6 because the required high-resolution isotopic measurements are very challenging. Our team is now addressing this challenge by developing the Potassium (K) - Argon Laser Experiment (KArLE) under the NASA Planetary Instrument Definition and Development Program (PIDDP), building on previous work to develop a K-Ar in situ instrument [1]. KArLE uses a combination of several flight-proven components that enable accurate K-Ar isochron dating of planetary rocks. KArLE will ablate a rock sample, determine the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measure the liberated Ar using quadrupole mass spectrometry (QMS), and relate the two by the volume of the ablated pit using an optical method such as a vertical scanning interferometer (VSI). Our preliminary work indicates that the KArLE instrument will be capable of determining the age of several kinds of planetary samples to +/-100 Myr, sufficient to address a wide range of geochronology problems in planetary science.

Cohen, Barbara A.↗

Dust Removal on Mars Using Laser-Induced Breakdown Spectroscopy

Dust coatings on the surface of Mars complicate and, if sufficiently thick, mask the spectral characteristics and compositional determination of underlying material from in situ and remote sensing instrumentation. The Laser-Induced Breakdown Spectroscopy (LIBS) portion of the Chemistry & Camera (ChemCam) instrument, aboard the Mars Science Laboratory (MSL) rover, will be the first active remote sensing technique deployed on Mars able to remove dust. ChemCam utilizes a 5 ns pulsed 1067 nm high-powered laser focused to less than 400 m diameter on targets at distances up to 7 m [1,2]. With multiple laser pulses, dust and weathering coatings can be remotely analyzed and potentially removed using this technique [2,3]. A typical LIBS measurement during MSL surface operations is planned to consist of 50 laser pulses at ~14 mJ, with the first 5 to 10 pulses used to analyze as well as remove any surface coating. Additionally, ChemCam's Remote Micro-Imager (RMI) is capable of resolving 200 m details at a distance of 2 m, or 1 mm at 10 m [1,4]. In this study, we report on initial laboratory experiments conducted to characterize the removal of dust coatings using similar LIBS parameters as ChemCam under Mars-like conditions. These experiments serve to better understand the removal of surface dust using LIBS and to facilitate the analysis of ChemCam LIBS spectral data and RMI images.

Graff, T. G.↗

A Comparison of Multivariate and Pre-Processing Methods for Quantitative Laser-Induced Breakdown Spectroscopy of Geologic Samples

The ChemCam instrument selected for the Curiosity rover is capable of remote laser-induced breakdown spectroscopy (LIBS).[1] We used a remote LIBS instrument similar to ChemCam to analyze 197 geologic slab samples and 32 pressed-powder geostandards. The slab samples are well-characterized and have been used to validate the calibration of previous instruments on Mars missions, including CRISM [2], OMEGA [3], the MER Pancam [4], Mini-TES [5], and Moessbauer [6] instruments and the Phoenix SSI [7]. The resulting dataset was used to compare multivariate methods for quantitative LIBS and to determine the effect of grain size on calculations. Three multivariate methods - partial least squares (PLS), multilayer perceptron artificial neural networks (MLP ANNs) and cascade correlation (CC) ANNs - were used to generate models and extract the quantitative composition of unknown samples. PLS can be used to predict one element (PLS1) or multiple elements (PLS2) at a time, as can the neural network methods. Although MLP and CC ANNs were successful in some cases, PLS generally produced the most accurate and precise results.

Anderson, R. B.↗

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.↗

Multivariate Methods for Prediction of Geologic Sample Composition with Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) uses pulses of laser light to ablate a material from the surface of a sample and produce an expanding plasma. The optical emission from the plasma produces a spectrum which can be used to classify target materials and estimate their composition. The ChemCam instrument on the Mars Science Laboratory (MSL) mission will use LIBS to rapidly analyze targets remotely, allowing more resource- and time-intensive in-situ analyses to be reserved for targets of particular interest. ChemCam will also be used to analyze samples that are not reachable by the rover's in-situ instruments. Due to these tactical and scientific roles, it is important that ChemCam-derived sample compositions are as accurate as possible. We have compared the results of partial least squares (PLS), multilayer perceptron (MLP) artificial neural networks (ANNs), and cascade correlation (CC) ANNs to determine which technique yields better estimates of quantitative element abundances in rock and mineral samples. The number of hidden nodes in the MLP ANNs was optimized using a genetic algorithm. The influence of two data preprocessing techniques were also investigated: genetic algorithm feature selection and averaging the spectra for each training sample prior to training the PLS and ANN algorithms. We used a ChemCam-like laboratory stand-off LIBS system to collect spectra of 30 pressed powder geostandards and a diverse suite of 196 geologic slab samples of known bulk composition. We tested the performance of PLS and ANNs on a subset of these samples, choosing to focus on silicate rocks and minerals with a loss on ignition of less than 2 percent. This resulted in a set of 22 pressed powder geostandards and 80 geologic samples. Four of the geostandards were used as a validation set and 18 were used as the training set for the algorithms. We found that PLS typically resulted in the lowest average absolute error in its predictions, but that the optimized MLP ANN and the CC ANN often gave results comparable to PLS. Averaging the spectra for each training sample and/or using feature selection to choose a small subset of wavelengths to use for predictions gave mixed results, with degraded performance in some cases and similar or slightly improved performance in other cases. However, training time was significantly reduced for both PLS and ANN methods by implementing feature selection, making this a potentially appealing method for initial, rapid-turn-around analyses necessary for Chemcam's tactical role on MSL. Choice of training samples has a strong influence on the accuracy of predictions. We are currently investigating the use of clustering algorithms (e.g. k-means, neural gas, etc.) to identify training sets that are spectrally similar to the unknown samples that are being predicted, and therefore result in improved predictions

Morris, Richard↗

The Argon Geochronology Experiment (AGE)

This viewgraph presentation reviews the Argon Geochronology Experiment (AGE). Potassium-Argon dating is shown along with cosmic ray dating exposure. The contents include a flow diagram of the Argon Geochronology Experiment, and schematic diagrams of the mass spectrometer vacuum system, sample manipulation mechanism, mineral heater oven, and the quadrupole ion trap mass spectrometer. The Laser-Induced Breakdown Spectroscopy (LIBS) Operation with elemental abundances is also described.

age dating↗