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NASA NTRS2012

Developement of the Potassium-Argon Laser Experiment (KArLE) 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. Thus far, radiometric geochronology of planetary samples has only been accomplishable in terrestrial laboratories on samples from dedicated sample return missions and meteorites. In situ instruments to measure rock ages have been proposed, but none have yet reached TRL 6, because isotopic measurements with sufficient resolution are challenging. We have begun work under the NASA Planetary Instrument Definition and Development Program (PIDDP) to develop the Potassium (K) - Argon Laser Experiment (KArLE), a novel combination of several flight-proven components that will enable accurate KAr isochron dating of planetary rocks. KArLE will ablate a rock sample, measure 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 measuring the volume of the abated pit using a optical methods 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. Additional benefits derive from the fact that each KArLE component achieves analyses common to most planetary surface missions.

Cohen, Barbara A.↗

NASA NTRS2012

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.↗

NASA NTRS2013

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.↗

NASA NTRS2014

Calcium Sulfate Characterized by ChemCam/Curiosity 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 [1;2] and (2) a Remote Micro Imager (RMI), for the imaging context of laser analysis [3]. 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 were seen [4;5]. ChemCam analysis demonstrate that those fracture fills consist of calcium sulfates [6].

Nachon, M.↗

NASA NTRS2014

Volume Measurements of Laser-generated Pits for in Situ Geochronology Using KArLE (Potassium-Argon Laser Experiment)

KArLE (Potassium-‐Argon Laser Experiment) has been developed for in situ planetary geochronology using the K - Ar (potassium-‐argon) isotope system, where material ablated by LIBS (Laser-‐Induced Breakdown Spectroscopy) is used to calculate isotope abundances. We are determining the accuracy and precision of volume measurements of these pits using stereo and laser microscope data to better understand the ablation process for isotope abundance calculations. If a characteristic volume can be determined with sufficient accuracy and precision for specific rock types, KArLE will prove to be a useful instrument for future planetary rover missions.

French, R. A.↗

NASA NTRS2014

In Situ Geochronology on the Mars 2020 Rover with KArLE (Potassium-Argon Laser Experiment)

If extinct and/or extant life is discovered on Mars, knowledge of the chronology of the biosphere will be of paramount importance. KArLE will provide absolute ages of Mars 2020 rocks, which will allow us to understand them in the context of Mars' geologic history, connect them to other landing sites, and compare Martian epochs of habitability with the Earth's history and evolution of life. KArLE significantly enhances the ability of Mars 2020 to meet its science objectives by performing in situ age dating on key lithologies, enabling targeted searches for ancient biosignatures and increasing the chances of identifying evidence for Martian microbial life. The KArLE investigation makes its measurements on a core sample obtained with the rover drill, inserted into a small, mechanically simple chamber, followed by interrogation by laser-induced breakdown spectroscopy (LIBS), mass spectrometry, and optical imaging. The KArLE experiment is flexible enough to accommodate any partner providing these instrument components, a creative approach that extends the ability of the Mars 2020 payload to accomplish an additional highly-desirable science measurement for low cost and risk and minimal extra hardware.

Cohen, B. A.↗

NASA NTRS2014

Chemical Evidence for Smectites and Zeolites on Mars: Criteria and Limitations

Aqueous alteration on Mars can produce a range of tell-tale secondary minerals [1]. Surface missions typically obtain detailed and highly localized element compositional information, but not always mineralogical information, whereas orbital missions deduce mineralogy from relatively high spatial resolution IR spectral mapping (decameters scale, for CRISM), but obtain element data only over much larger areas of martian terrain (~200 km). Surface missions have also discovered several occurrences of major geochemical alteration of igneous precursors, for many of which elemental compositional is the only diagnostic information available. Many types of clays and zeolites have quasi-unique element profiles which may be used to implicate their presence. In some cases, one or more candidate minerals are sufficiently close in their component elements and their stoichiometry that ambiguity must remain, unless other constraints can be brought to bear. Geochemical characteristics of alteration products most likely on Mars can be compared to results from MER and MSL rover missions (e.g. Independence [4] and Esperance samples). These considerations are needed for MER Opportunity rover now that Mini-TES is no longer operational. It also has importance for exploration by the MSL Curiosity rover because inferences and deductions available from ChemCam (CCAM) remote LIBS and/or in situ x-ray fluorescence (APXS) can be used as indicators for triage to select materials to sample for limited-resource instruments, SAM and Chemin.

Clark, B. C.↗

NASA NTRS2014

The Potassium-Argon Laser Experiment (KarLE): In Situ Geochronology for Mars and Beyond

The search for life in the solar system depends upon discovering the right moments in planetary evolution: when habitable environments existed, when they declined, and when geologic processes operated to preserve traces of life after death. However, an incomplete knowledge of absolute Martian geochronology limits our ability to understand the timing of Martian evolutionary milestones, major climate changes, and stratigraphic epochs [1, 2]. Absolute dating relates these habitability markers to planetarywide geologic, atmospheric, and climate history places, and ties their occurrence to the history of the solar system, especially the Earth-Moon system and the timescale of evolution of life on Earth. KArLE is being developed to anchor the relative timeline of geological events to an absolute chronology that puts Mars into a wider solar system context. KArLE makes its measurements on rock samples that can be obtained by landers or rovers and inserted into a small, mechanically simple chamber. KArLE interrogates the samples using laser-induced breakdown spectrocopy (LIBS), mass spectrometry, and optical imaging. The KArLE experiment is flexible enough to accommodate any partner providing these instrument components, a creative approach that extends the ability of mission payloads to accomplish an additional highly-desirable science measurement for low cost and risk and minimal extra hardware.

Cohen, Barbara A.↗

NASA NTRS2014

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.↗

NASA NTRS2014

The Potassium-Argon Laser Experiment (KARLE): In Situ Geochronology for Planetary Robotic Missions

Isotopic dating is an essential tool to establish an absolute chronology for geological events, including crystallization history, magmatic evolution, and alteration events. The capability for in situ geochronology will open up the ability for geochronology to be accomplished as part of lander or rover complement, on multiple samples rather than just those returned. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. The K-Ar Laser Experiment (KArLE) brings together a novel combination of several flight-proven components to provide precise measurements of potassium (K) and argon (Ar) that will enable accurate isochron dating of planetary rocks. KArLE will ablate a rock sample, measure the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measure the liberated Ar using mass spectrometry (MS), and relate the two by measuring the volume of the ablated pit by optical imaging. Our work indicates that the KArLE instrument is capable of determining the age of planetary samples with sufficient accuracy to address a wide range of geochronology problems in planetary science. Additional benefits derive from the fact that each KArLE component achieves analyses useful for most planetary surface missions.

Cohen, B. A.↗

NASA NTRS2015

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.↗

NASA NTRS2015

Continued Development of in Situ Geochronology for Planetary Missions

The instrument 'Potassium (K) Argon Laser Experiment' (KArLE) is developed and designed for in situ absolute dating of rocks on planetary surfaces. It is based on the K-Ar dating method and uses the Laser Induced Breakdown Spectroscopy - Laser Ablation - Quadrupole Mass Spectrometry (LIBSLA- QMS) technique. We use a dedicated interface to combine two instruments similar to SAM of Mars Science Laboratory (for the QMS) and ChemCam (for the LA and LIBS). The prototype has demonstrated that KArLE is a suitable and promising instrument for in situ absolute dating.

geochronology↗

NASA NTRS2016

Continued Development of in Situ Geochronology for Planetary Using KArLE (Potassium-Argon Laser Experiment)

Geochronology is a fundamental measurement for planetary samples, providing the ability to establish an absolute chronology for geological events, including crystallization history, magmatic evolution, and alteration events, and providing global and solar system context for such events. The capability for in situ geochronology will open up the ability for geochronology to be accomplished as part of lander or rover complement, on multiple samples rather than just those returned. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. The K-Ar radiometric dating approach to in situ dating has been validated by the Curiosity rover on Mars as well as several laboratories on Earth. Several independent projects developing in situ rock dating for planetary samples, based on the K-Ar method, are giving promising results. Among them, the Potassium (K)-Argon Laser Experiment (KArLE) at MSFC is based on techniques already in use for in planetary exploration, specifically, Laser-induced Breakdown Spectroscopy (LIBS, used on the Curiosity Chemcam), mass spectroscopy (used on multiple planetary missions, including Curiosity, ExoMars, and Rosetta), and optical imaging (used on most missions).

In SITU Geochronology↗

NASA NTRS2015

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

cathodes↗

NASA NTRS2015

Mineralogy and Astrobiology Detection Using Laser Remote Sensing Instrument

A multispectral instrument based on Raman, laser-induced fluorescence (LIF), laser-induced breakdown spectroscopy (LIBS), and a lidar system provides high-fidelity scientific investigations, scientific input, and science operation constraints in the context of planetary field campaigns with the Jupiter Europa Robotic Lander and Mars Sample Return mission opportunities. This instrument conducts scientific investigations analogous to investigations anticipated for missions to Mars and Jupiter's icy moons. This combined multispectral instrument is capable of performing Raman and fluorescence spectroscopy out to a >100 m target distance from the rover system and provides single-wavelength atmospheric profiling over long ranges (>20 km). In this article, we will reveal integrated remote Raman, LIF, and lidar technologies for use in robotic and lander-based planetary remote sensing applications. Discussions are focused on recently developed Raman, LIF, and lidar systems in addition to emphasizing surface water ice, surface and subsurface minerals, organics, biogenic, biomarker identification, atmospheric aerosols and clouds distributions, i.e., near-field atmospheric thin layers detection for next robotic-lander based instruments to measure all the above-mentioned parameters. OCIS codes: (120.0280) Remote sensing and sensors; (130.0250) Optoelectronics; (280.3640) Lidar; (300.2530) Fluorescence, laser-induced; (300.6450) Spectroscopy, Raman; (300.6365) Spectroscopy, laser induced breakdown

Abedin, M. Nurul↗

NASA NTRS2016

Design and Calibration of a Raman Spectrometer for use in a Laser Spectroscopy Instrument Intended to Analyze Martian Surface and Atmospheric Characteristics for NASA

This project's goal is the design of a Raman spectroscopy instrument to be utilized by NASA in an integrated spectroscopy strategy that will include Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Induced Florescence Spectroscopy (LIFS) for molecule and element identification on Mars Europa, and various asteroids. The instrument is to be down scaled from a dedicated rover mounted instrument into a compact unit with the same capabilities and accuracy as the larger instrument. The focus for this design is a spectrometer that utilizes Raman spectroscopy. The spectrometer has a calculated range of 218 nm wavelength spectrum with a resolution of 1.23 nm. To filter out the laser source wavelength of 532 nm the spectrometer design utilizes a 532 nm wavelength dichroic mirror and a 532 nm wavelength notch filter. The remaining scatter signal is concentrated by a 20 x microscopic objective through a 25-micron vertical slit into a 5mm diameter, 1cm focal length double concave focusing lens. The light is then diffracted by a 1600 Lines per Millimeter (L/mm) dual holographic transmission grating. This spectrum signal is captured by a 1-inch diameter double convex 3 cm focal length capture lens. An Intensified Charge Couple Device (ICCD) is placed within the initial focal cone of the capture lens and the Raman signal captured is to be analyzed through spectroscopy imaging software. This combination allows for accurate Raman spectroscopy to be achieved. The components for the spectrometer have been bench tested in a series of prototype developments based on theoretical calculations, alignment, and scaling strategies. The mounting platform is 2.5 cm wide by 8.8 cm long by 7 cm height. This platform has been tested and calibrated with various sources such as a neon light source and ruby crystal. This platform is intended to be enclosed in a ruggedized enclosure for mounting on a rover platform. The size and functionality of the Raman spectrometer allows for the rover to carry other mission critical devices. This project will be continued at NASA until the requirements are met for the expected initial 2020 launch date.

Lucas, John F.↗

NASA NTRS2018

Laser Ablation Surface Treatment of Structural Aerospace Composites and Metal Alloys for Adhesive Bonding

NASA Langley Research Center (LaRC) has been involved over the past decade in the development of laser ablation as a method to surface treat aerospace structural fiber reinforced composites (CFRPs) and metal alloys. [1- 18] Laser surface treatment has been shown to be a rapid, high precision, and reproducible method for surface treatment of these materials, and is amenable to automation. The laser ablation process removes surface contamination such as silicones, creates surface roughness, and chemically activates a surface for bonding. The degree of ablation is controllable by adjusting laser parameters. In the case of CFRPs, ablation can be performed without damage to any underlying carbon fibers. In the case of metal alloys, ablation is possible without surface embrittlement, heat damage or creation of undesirable grain structures or morphologies. The optimum laser treatment conditions are substrate dependent and generally are influenced by laser wavelength and pulse duration (typically fixed for a laser system), and laser power. In the case of metal alloys such as Ti-6Al-4V, the laser ablation process eliminates the need for several steps of the conventional processes, including hydrofluoric (HF) acid and caustic treatment. These steps are often conducted in dip tanks and require costly facilities and environmentally unfriendly liquids. In addition, the laser can create nano-porosity on the Ti-6Al-4V alloy surface allowing for sol-gel penetration and thereby creating a gradient interface with improved temperature and mechanical performance. NASA LaRC has also been involved with the development of in-line characterization methods compatible with the laser treatment process to rapidly determine the presence of key contaminates such as silicones that, even at very low concentrations, are a threat to adhesive bonding. A spectroscopic technique called micro-laser induced breakdown spectroscopy (u-LIBS) has been developed to rapidly detect silicones at concentrations below those known to cause bonding problems. This technique requires no sample preparation, vacuum or inert atmosphere, has no practical size limitations, and provides nearly instantaneous feedback to the operator. This presentation will give an overview and update of these developments with specific examples highlighted.

Connell, John W.↗

NASA NTRS2018

Design and Development of Advanced Air-Cathodes for Li-Air Battery

NASA's future missions demand high energy density batteries. Current state-of-the-art lithium-ion batteries (LIBs) reach the specific energy capacity limits (<250 Wh/kg), thus new electrochemical storage technologies are needed to meet NASA's future mission requirement of >400 Wh/kg. Battery chemistries with higher theoretical energy densities in particular, Li-metal based battery chemistries such as Li-air, are being actively pursued, but there remains a number of issues to be solved. Development of advanced and optimized air cathodes will be crucial for improving capacity retention and cycle life of Li-air battery. The microstructure of carbon substrates and the catalytic oxygen reduction of the air-cathode play critical roles in the electrochemical performance in Li-air batteries. With the development and proper design of air cathodes, the energy efficiency and energy density can be enhanced significantly. In this presentation, the results of advanced permeable air cathodes design with different substrates such as 2D carbon paper or carbon cloth, vs 3D graphene or metal foam, different high surface area carbon materials and incorporation with catalysts on oxygen reduction reactions, different porosity controlling of air cathode as well the additives in electrolyte will be presented. The cycling and rate capability performance of these air-cathodes in the Li-air cells will be discussed as well.

Wu, James J.↗