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Integration of LIBS with Machine Learning for Real-Time Monitoring of Feedstock in H 2 Gasification Applications

This project, funded by the U.S. Department of Energy (DOE) – Office of Fossil Energy under Award Number DE-FE0032177, aimed to assess the feasibility of an integrated Laser-Induced Breakdown Spectroscopy (LIBS) system with advanced machine learning (ML) models for real-time characterization and potential control of hydrogen gasifiers running on waste materials as feedstocks. This was a multidisciplinary effort that encompassed the acquisition and standardized analysis of individual and blended feedstocks—comprising biomass, coal waste, and plastic waste, followed by the development of a dynamic LIBS bench system for material sample analysis and development of predictive ML models. Comprehensive laboratory testing enabled the creation of a robust elemental dataset that served as the foundation for ML model training. Techniques such as Random Forest, Gradient Boosting, Support Vector Regression, and Neural Networks were employed to predict key feedstock properties, including higher heating value (HHV), moisture content, thermal conductivity, and ash composition with high accuracy. The results were validated against experimental data and demonstrated strong potential for real-time application in gasifier control systems. The project concluded with a study on the integration of the LIBS+ML approach for gasifier control and a techno-economic analysis of the implementation of the approach into hydrogen (H 2 ) gasification systems. Dissemination of results was carried out at a DOE meeting. This work establishes a scalable framework for automated, in-line feedstock quality assessment, offering significant implications for process optimization and emissions reduction in hydrogen production.

01 COAL, LIGNITE, AND PEAT↗

MPEX AI Digital Twins

All magnetically confined plasma fusion power plant concepts (Tokamak, Spherical Tokamak, Stellarator, Mirror, ...) must exhaust the heat and plasma from the core confinement region to the material walls. The primary channel for this exhaust is through a plasma divertor which directs plasma along open magnetic field lines to a material target. The Material Plasma Exposure eXperiment (MPEX) illustrated in Figure 1, is a high-power, steady-state linear plasma device designed to produce the plasma material interaction (PMI) conditions of the divertor of future magnetic confinement fusion power plants: energy flux 20MW/m 2 , ion fluence 1031/m 2 , pulse duration 106 sec. These goals of plasma exposure in MPEX are well beyond those achieved in magnetic fusion experimental devices. Successfully achieving these high power steady state conditions for long pulses requires operational control of the heating and particle sources and the plasma flux to the walls and target. The MPEX AI Hot Spot Controller, proposed in this project, will help achieve the operational milestones of MPEX. The MPEX device will begin commissioning at the end of FY26. A smaller proto-MPEX was operated for 14,666 plasma discharges and will resume operation in September of 2025 as proto-MPEX-lite, with reduced capability, to test a new window for the Helicon plasma source. The proto-MPEX data has undergone surrogate modeling with machine learning methods (R. Archibald, 2022 IEEE International Conference on Big Data). This proto-MPEX data will be used to begin development of the AI digital twins described in this white paper. The scientific mission of MPEX is to qualify materials of different composition for use in the high energy and plasma flux conditions of a fusion power plant. The materials exposed in MPEX will in some cases be exposed to high neutron fluxes at other ORNL facilities to measure the changes to their PMI properties. The targets exposed in MPEX will be transported under vacuum to a Surface Analysis Station (SAS). The SAS will be equipped with the following diagnostics: Focused Ion Beam (FIB) for trench milling, 100-400 angstrom resolution scanning electron microscope (SEM), surface mapping x-ray spectrometer, high resolution camera, and a future upgrade to a laser induced breakdown spectroscopy quadruple mass spectrometer (LIBS-QMS). The MPEX experiments will generate diverse pre- and post-exposure measurement data of detailed material properties down to the crystal grain level in 3D for post-exposure assessment of PMI damage (e.g. cracking, melting, erosion and redeposition of the material). Physics models for the PMI, and how the material composition and manufacturing impact its performance under high energy plasma exposure, need to be validated with MPEX data to guide the selection of new candidate materials. Our vision for the MPEX AI Digital Twins project is to supply experimental and physics model simulation data to train Artificial Intelligence (AI) models for data processing, analysis, operational control, PMI and materials simulation to maximize the scientific output of the MPEX device. Ultimately, an AI digital twin of MPEX material assessment metrics for tested and synthetic material types with simulated PMI will be trained by the AI Modeling Teams on the experimental and physics simulation data submitted to the American Science Cloud by this project. A purely empirical search for the best material is inefficient given the finite number of samples that can be tested on MPEX. In order to expand the material properties database for training the MPEX Material Assessment AI Digital Twin, and to gain physics understanding of the PMI processes, physics models of the material properties and PMI processes are required. The physics simulations provide detailed simulation data, like impact angles for plasma ions, sputtering yields, transport of the ionized sputtered target material in the plasma, and redeposition locations. This simulation data expands the measurement data for deeper physics understanding. The experimental data is essential to validate the PMI and material structure simulation models. The validated models can then be used to generate new simulation data of MPEX material assessments for synthetic material compositions that have not been exposed in MPEX. These predictive simulations, plus the whole experimental dataset, will be used to train the MPEX Material Assessment AI Digital Twin allowing a rapid generative AI search for new materials with reduced PMI damage by interpolating the domain of the training set. These new optimum materials can be simulated with the physics codes and/or tested in MPEX. The ability of AI neural networks to interpolate multi-dimensional parameter spaces and generate virtual data is exploited for a more efficient search for optimum materials. The advent of the Transformational AI Models Consortium (TAIMC) is an opportunity to engage with state of the art private and public AI developers to achieve the goals of the AI digital twins and AI accelerated physics models proposed in this project. Our partners at ORNL from the Advance Scientific Computing Research (ASCR) organization will collaborate in accelerating the integrated plasma material interaction simulation framework. This simulation framework will provide a platform for generating simulation data across a range of physical fidelities, including hybrid methods that produce multi-fidelity results. This data will be leveraged for AI model development, both for generation of surrogates and the automation of simulation campaigns. A part of the research below will include collaborative efforts with the TAIMC to (i) adapt data storage approaches to ensure AI-readiness, (ii) provide a protypical exemplar to inform and exercise constructed workflows, and (iii) generate and share data, using the TAIMC unified AI data standard, for foundational models that will be trained from multiple sources across the DOE complex. We will also collaborate with the TAIMC, as well as the planned AI modeling teams, to develop approaches for reducing the cost of data generation. These include tailored multi-fidelity approaches as well as fine-tuning strategies to augment general, large-scale foundational models.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

ATOMIC Simulations and Experimental Data for Sodium and Copper Mixtures

This data consists of simulations and experimental measurements of laser-induced breakdown spectroscopy (LIBS). The simulations are produced by ATOMIC, a general purpose plasma modeling and kinetics code that has been designed to compute emission (or absorption) spectra from plasmas [1]. Our overall suite of simulations contains 12 sets of simulations: training and validation sets of simulations for each of two resolutions of each of sodium, copper, and mixtures of the two. The training data were produced using a 500-run design that varies input parameters temperature (T), electron density (Ne), proportion of sodium (pNa), and proportion of copper (pCu). The latter two variables sum to one and are unused in the single-element simulations. The validation data was produced with a 25-run design. The coarse simulations produce spectra over a range of 240nm - 880nm that roughly mimics the range collected by the ChemCam instrument on the Mars rover Curiosity. The fine resolution simulations produce spectra over a range of 550nm to 600nm and were produced to mimic the included experimental results. The experimental results cover four mixtures of sodium and copper. All data sets are kept in zip files whose names indicate the elemental composition (NaCu, Na, or Cu), resolution (coarse or fine), and purpose (training or validation) with file names numbered to indicate the line in the design files used to produce the simulation. The designs are provided as text files with names indicating their purpose. The experimental data is provided as a CSV file. See attached abstract for figures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Lunar and Planetary Science XXXV: Venus

The session "Venus" included the following reports:Preliminary Study of Laser-induced Breakdown Spectroscopy (LIBS) for a Venus Mission; Venus Surface Investigation Using VIRTIS Onboard the ESA/Venus Express Mission; Use of Magellan Images for Venus Landing Safety Assessment; Volatile Element Geochemistry in the Lower Atmosphere of Venus; Resurfacing Styles and Rates on Venus: Assessment of 18 Venusian Quadrangles; Stereo Imaging of Impact Craters in the Beta-Atla-Themis (BAT) Region, Venus; Depths of Extended Crater-related Deposits on Venus ; Potential Pyroclastic Deposit in the Nemesis Tessera (V14) Quadrangle of Venus; Relationship Between Coronae, Regional Plains and Rift Zones on Venus, Preliminary Results; Coronae of Parga Chasma, Venus; The Evolution of Four Volcano/Corona Hybrids on Venus; Calderas on Venus and Earth: Comparison and Models of Formation; Venus Festoon Deposits: Analysis of Characteristics and Modes of Emplacement; Topographic and Structural Analysis of Devana Chasma, Venus: A Propagating Rift System; Anomalous Radial Structures at Irnini Mons, Venus: A Parametric Study of Stresses on a Pressurized Hole; Analysis of Gravity and Topography Signals in Atalanta-Vinmara and Lavinia Planitiae Canali are Lava, Not River, Channels; and Formation of Venusian Channels in a Shield Paint Substrate.

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Lunar and Planetary Science XXXV: Missions and Instruments: Hopes and Hope Fulfilled

The titles in this section include: 1) Mars Global Surveyor Mars Orbiter Camera in the Extended Mission: The MOC Toolkit; 2) Mars Odyssey THEMIS-VIS Calibration; 3) Early Science Operations and Results from the ESA Mars Express Mission: Focus on Imaging and Spectral Mapping; 4) The Mars Express/NASA Project at JPL; 5) Beagle 2: Mission to Mars - Current Status; 6) The Beagle 2 Microscope; 7) Mars Environmental Chamber for Dynamic Dust Deposition and Statics Analysis; 8) Locating Targets for CRISM Based on Surface Morphology and Interpretation of THEMIS Data; 9) The Phoenix Mission to Mars; 10) First Studies of Possible Landing Sites for the Phoenix Mars Scout Mission Using the BMST; 11) The 2009 Mars Telecommunications Orbiter; 12) The Aurora Exploration Program - The ExoMars Mission; 13) Electron-induced Luminescence and X-Ray Spectrometer (ELXS) System Development; 14) Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice; 15) The Compact Microimaging Spectrometer (CMIS): A New Tool for In-Situ Planetary Science; 16) Preliminary Results of a New Type of Surface Property Measurement Ideal for a Future Mars Rover Mission; 17) Electrodynamic Dust Shield for Solar Panels on Mars; 18) Sensor Web for Spatio-Temporal Monitoring of a Hydrological Environment; 19) Field Testing of an In-Situ Neutron Spectrometer for Planetary Exploration: First Results; 20) A Miniature Solid-State Spectrometer for Space Applications - Field Tests; 21) Application of Laser Induced Breakdown Spectroscopy (LIBS) to Mars Polar Exploration: LIBS Analysis of Water Ice and Water Ice/Soil Mixtures; 22) LIBS Analysis of Geological Samples at Low Pressures: Application to Mars, the Moon, and Asteroids; 23) In-Situ 1-D and 2-D Mapping of Soil Core and Rock Samples Using the LIBS Long Spark; 24) Rocks Analysis at Stand Off Distance by LIBS in Martian Conditions; 25) Evaluation of a Compact Spectrograph/Detection System for a LIBS Instrument for In-Situ and Stand-Off Detection; 26) Analysis of Organic Compounds in Mars Analog Samples; 27) Report of the Organic Contamination Science Steering Group; 28) The Water-Wheel IR (WIR) - A Contact Survey Experiment for Water and Carbonates on Mars; 29) Mid-IR Fiber Optic Probe for In Situ Water Detection and Characterization; 30) Effects of Subsurface Sampling & Processing on Martian Simulant Containing Varying Quantities of Water; 31) The Subsurface Ice Probe (SIPR): A Low-Power Thermal Probe for the Martian Polar Layered Deposits; 32) Deploying Ground Penetrating Radar in Planetary Analog Sites to Evaluate Potential Instrument Capabilities on Future Mars Missions; 33) Evaluation of Rock Powdering Methods to Obtain Fine-grained Samples for CHEMIN, a Combined XRD/XRF Instrument; 34) Novel Sample-handling Approach for XRD Analysis with Minimal Sample Preparation; 35) A New Celestial Navigation Method for Mars Landers; 36) Mars Mineral Spectroscopy Web Site: A Resource for Remote Planetary Spectroscopy.

Source record↗

Lunar and Planetary Science XXXVI, Part 18

Topics discussed include: PoDS: A Powder Delivery System for Mars In-Situ Organic, Mineralogic and Isotopic Analysis Instruments Planetary Differentiation of Accreting Planetesimals with 26Al and 60Fe as the Heat Sources Ground-based Observation of Lunar Surface by Lunar VIS/NIR Spectral Imager Mt. Oikeyama Structure: First Impact Structure in Japan? Central Mounds in Martian Impact Craters: Assessment as Possible Perennial Permafrost Mounds (Pingos) A Further Analysis of Potential Photosynthetic Life on Mars New Insight into Valleys-Ocean Boundary on Mars Using 128 Pixels per Degree MOLA Data: Implication for Martian Ocean and Global Climate Change; Recursive Topography Based Surface Age Computations for Mars: New Insight into Surficial Processes That Influenced Craters Distribution as a Step Toward the Formal Proof of Martian Ocean Recession, Timing and Probability; Laser-induced Breakdown Spectroscopy: A New Method for Stand-Off Quantitative Analysis of Samples on Mars; Milk Spring Channels Provide Further Evidence of Oceanic, >1.7-km-Deep Late Devonian Alamo Crater, Southern Nevada; Exploration of Martian Polar Residual Caps from HEND/ODYSSEY Data; Outflow Channels Influencing Martian Climate: Global Circulation Model Simulations with Emplaced Water; Presence of Nonmethane Hydrocarbons on Pluto; Difference in Degree of Space Weathering on the Newborn Asteroid Karin; Circular Collapsed Features Related to the Chaotic Terrain Formation on Mars; A Search for Live (sup 244)Pu in Deep-Sea Sediments: Preliminary Results of Method Development; Some Peculiarities of Quartz, Biotite and Garnet Transformation in Conditions of Step-like Shock Compression of Crystal Slate; Error Analysis of Remotely-Acquired Mossbauer Spectra; Cloud Activity on Titan During the Cassini Mission; Solar Radiation Pressure and Transient Flows on Asteroid Surfaces; Landing Site Characteristics for Europa 1: Topography; and The Crop Circles of Europa.

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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↗

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.↗

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.↗

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.↗

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.↗

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.↗

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

The Potassium (K) - Argon (Ar) Laser Experiment (KArLE) will make in situ noble-gas geochronology measurements aboard planetary robotic landers and roverss. Laser-Induced Breakdown Spectroscopy (LIBS) is used to measure the K abun-dance in a sample and to release its noble gases; the evolved Ar is measured by mass spectrometry (MS); and rela-tive K content is related to absolute Ar abundance by sample mass, determined by optical measurement of the ablated volume. KArLE measures a whole-rock K-Ar age to 10% or better for rocks 2 Ga or older, sufficient to resolve the absolute age of many planetary samples. The LIBS-MS approach is attractive because the analytical components have been flight proven, do not require further technical development, and provide complementary measurements as well as in situ geochronology.

KArLE↗

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↗

Picosecond Pulsed Laser Ablation for the Surface Preparation of Epoxy Composites

As part of a technical challenge under the Advanced Composites Program, methods for improving pre-bond process control for aerospace composite surface treatments and inspections, in conjunction with Federal Aviation Administration guidelines, are under investigation. The overall goal is to demonstrate high fidelity, rapid and reproducible surface treatment and surface characterization methods to reduce uncertainty associated with the bonding process. The desired outcomes are reliable bonded airframe structure, and reduced timeline to certification. In this work, laser ablation was conducted using a q-switched Nd:YVO4 laser capable of nominal pulse durations of 8 picoseconds (ps). Aerospace structural carbon fiber reinforced composites with an epoxy resin matrix were laser treated, characterized, processed into bonded assemblies and mechanically tested. The characterization of ablated surfaces were conducted using scanning electron microscopy (SEM), water contact angle (WCA) goniometry, micro laser induced breakdown spectroscopy (uLIBS), and electron spin resonance (ESR). The bond performance was assessed using a double cantilever beam (DCB) test with an epoxy adhesive. The surface characteristics and bond performance obtained from picosecond ablated carbon fiber reinforced plastics (CFRPs) are presented herein.

Palmieri, Frank↗

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.↗

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.↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗