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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↗

Development and Testing of Laser-induced Breakdown Spectroscopy for the Mars Rover Program: Elemental Analyses at Stand-Off Distances

One of the most fundamental pieces of information about any planetary body is the elemental composition of its surface materials. The Viking Martian landers employed XRF (x-ray fluorescence) and the MER rovers are carrying APXS (alpha-proton x-ray spectrometer) instruments upgraded from that used on the Pathfinder rover to supply elemental composition information for soils and rocks to which direct contact is possible. These in- situ analyses require that the lander or rover be in contact with the sample. In addition to in-situ instrumentation, the present generation of rovers carry instruments that operate at stand-off distances. The Mini-TES is an example of a stand-off instrument on the MER rovers. Other examples for future missions include infrared point spectrometers and microscopic-imagers that can operate at a distance. The main advantage of such types of analyses is obvious: the sensing element does not need to be in contact or even adjacent to the target sample. This opens up new sensing capabilities. For example, targets that cannot be reached by a rover due to impassable terrain or targets positioned on a cliff face can now be accessed using stand-off analysis. In addition, the duty cycle of stand-off analysis can be much greater than that provided by in-situ measurements because the stand-off analysis probe can be aimed rapidly at different features of interest eliminating the need for the rover to actually move to the target. Over the past five years we have been developing a stand-off method of elemental analysis based on atomic emission spectroscopy called laser-induced breakdown spectroscopy (LIBS). A laser-produced spark vaporizes and excites the target material, the elements of which emit at characteristic wavelengths. Using this method, material can be analyzed from within a radius of several tens of meters from the instrument platform. A relatively large area can therefore be sampled from a simple lander without requiring a rover or sampling arms. The placement of such an instrument on a rover would allow the sampling of locations distant from the landing site. Here we give a description of the LIBS method and its advantages. We discuss recent work on determining its characteristics for Mars exploration, including accuracy, detection limits, and suitability for determining the presence of water ice and hydrated minerals. We also give a description of prototype instruments we have tested in field settings.

D A Cremers↗

Laser-Induced Breakdown Spectroscopy of Trace Metals

An alternative approach for laser-induced breakdown spectroscopy (LIBS) determination of trace metal determination in liquids is demonstrated. The limits of detection (LOD) for the technique ranged from 10 ppb to 10 ppm for 15 metals metals (Mg, Al, Si, Ca, Ti, Cr, Fe, Co, Ni, Cu, Zn, As, Cd, Hg, Pb) tested.

Simons, Stephen↗

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.↗

Post-Landing Major Element Quantification Using SuperCam Laser Induced Breakdown Spectroscopy

The SuperCam instrument on the PerseveranceMars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions andspectra are normalized to minimize signal fluctuations and effectsof target distance.In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositionsof diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g.,silicates, sulfates, carbonates, oxides),more unusual compositions (e.g.,Mn oreand sodalite), andreplicates of the sintered SuperCam calibration targets (SCCTs) onboardthe rover. For each major element (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), the database was subdivided into five“folds” with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining fourfolds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

Mars 2020↗

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.↗

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.↗

Surface Characterization of Carbon Fiber Reinforced Polymers by Picosecond Laser Induced Breakdown Spectroscopy

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants as part of a vigorous quality control process to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding are essential in order to obtain a surface which is free from contaminants that may lead to inferior bond quality. In this study, the focus is to advance the laser induced breakdown spectroscopy (LIBS) technique by using pulse energies below 100 μJ (μLIBS) for the detection of low levels of silicone contaminants in carbon fiber reinforced polymer (CFRP) composites. Various CFRP surface conditions were investigated by LIBS using ∼10 ps, 355 nm laser pulses with pulse energies below 30 μJ. Time-resolved analysis was conducted to optimize the gate delay and gate width for the detection of the C I emission line at 247.9 nm to monitor the epoxy resin matrix of CFRP composites and the Si I emission line at 288.2 nm for detection of silicone contaminants in CFRP. To study the surface sensitivity to silicone contamination, CFRP surfaces were coated with polydimethylsiloxane (PDMS), the active ingredient in many mold release agents. The presence of PDMS was studied by inspecting the Si I emission lines at 251.6 nm and 288.2 nm. The measured PDMS areal densities ranged from 0.15 to 2 μg/cm(sup 2). LIBS measurements were performed before and after laser surface ablation. The results demonstrate the successful detection of PDMS thin layers on CFRP using picosecond μLIBS.

Rodolfo Ledesma↗

Unreported Emission Lines of Rb, Ce, La, Sr, Y, Zr, Pb and Se Detected Using Laser-Induced Breakdown Spectroscopy

Information on emission lines for major and minor elements is readily available from the National Institute of Standards and Technology (NIST) as part of the Atomic Spectra Database. However, tabulated emission lines are scarce for some minor elements and the wavelength ranges presented on the NIST database are limited to those included in existing studies. Previous work concerning minor element calibration curves measured using laser-induced break-down spectroscopy found evidence of Zn emission lines that were not documented on the NIST database. In this study, rock powders were doped with Rb, Ce, La, Sr, Y, Zr, Pb and Se in concentrations ranging from 10 percent to 10 parts per million. The difference between normalized spectra collected on samples containing 10 percent dopant and those containing only 10 parts per million were used to identify all emission lines that can be detected using LIBS (Laser-Induced Breakdown Spectroscopy) in a ChemCam-like configuration at the Mount Holyoke College LIBS facility. These emission spectra provide evidence of many previously undocumented emission lines for the elements measured here.

LIBS↗

Closed-Loop Control of Laser Surface Treatment via Laser Induced Breakdown Spectroscopy

Current composite manufacturing rates need to be improved to meet the projected demand of on-demand mobility (ODM) and commercial aircraft transports. Some processes in the composite manufacturing chain require touch labor such as manual sanding of surfaces prior to bonding and installing thousands of mechanical fasteners in bonded primary structures to achieve Federal Aviation Administration (FAA) certification. The consequences are insufficient repeatability in bond quality resulting in increased manufacturing time. The FAA has indicated that robust process control is one potential means of certifying bondlines in primary structure. This work describes an integrated closed-loop control system between a laser machining system and laser induced breakdown spectroscopy (LIBS) instrumentation as a means of assuring bond performance and achieving certified composite bondlines. Preliminary results from in-situ treatment and inspection are presented. Results indicate that LIBS inspection and laser treatment can be conducted simultaneously to achieve high quality, reliable adhesive bonds.

Rodolfo Ledesma↗

Closed-Loop Control of Laser Surface Treatment via Laser Induced Breakdown Spectroscopy

Current composite manufacturing rates need to be improved to meet the projected demand of on-demand mobility (ODM) and commercial aircraft transports. Some processes in the composite manufacturing chain require touch labor such as manual sanding of surfaces prior to bonding and installing thousands of mechanical fasteners in bonded primary structures to achieve Federal Aviation Administration (FAA) certification. The consequences are insufficient repeatability in bond quality resulting in increased manufacturing time. The FAA has indicated that robust process control is one potential means of certifying bondlines in primary structure. This work describes an integrated closed-loop control system between a laser machining system and laser induced breakdown spectroscopy (LIBS) instrumentation as a means of assuring bond performance and achieving certified composite bondlines. Preliminary results from in-situ treatment and inspection are presented. Results indicate that LIBS inspection and laser treatment can be conducted simultaneously to achieve high quality, reliable adhesive bonds.

Rodolfo Ledesma↗

Standards for Analysis of Ce, La, Pb, Rb, Se, Sr, Y, AND Zr in Rock Samples Using Laser-induced Breakdown Spectroscopy and X-ray Fluorescence

Analytical geochemistry has long depended on the availability of robust suites of rock standards with well-characterized compositions. Standard rock powders for wet chemistry and x-ray fluorescence were initially characterized and supplied to the community by the U.S. Geological Survey, which continues to distribute a few dozen standards. Many other rock standards have subsequently been developed by organizations such as the Centre de Recherches Pétrographiques et Géochimiques (CRPG) and Brammer Standard Company, Inc.

LIBS↗

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↗