ARTIFICIAL NEURAL-NETWORK; ICP-MS; LASER; LIBS; PLASMA; MATRIX; MODEL

Laser-induced breakdown spectroscopy can be used for measuring the concentrations or ratios of various trace elements in solid samples. A laser pulse with a 532 nm wavelength, 5 ns pulse duration, 100 mm beam spot diameter, and 30 mJ single pulse energy is used for ablating the United States Geological Survey series of geological standard samples. The concentrations of iron in different geological samples are obtained using artificial neural networks. In addition, the influence of matrix effects on the measurement error is analyzed. Experimental results reveal that the relative errors of BCR-1G, BHVO-2G, BIR-1G, GSD-1G, and GSE-1G between the measured concentrations and the certified concentrations are 1.86%, 5.73%, 0.27%, 3.86%, and 2.63%, respectively, which indicate that the LIBS method using back propagation artificial neural networks can effectively determine the iron concentrations of USGS geological standard samples. The matrix effects of standard samples are analyzed, which shows that the matrix effects of GSD-1G and GSE-1G are more different than others. As a result, some significant measurement errors in concentration determination resulted from different matrix effects.

Laser-induced breakdown spectroscopy; LIBS; Variable angle; Incidence angle; Collection angle; Partial least-squares analysis; PLS;

Laser-induced breakdown spectroscopy has become a popular tool for rapid elemental analysis of geological materials. However, quantitative applications of LIBS are plagued by variability in collected spectra that cannot be attributed to differences in geochemical composition. Even under ideal laboratory conditions, variability in LIBS spectra creates a host of difficulties for quantitative analysis. This is only exacerbated during field work, when both the laser-sample distance and the angle of ablation/collection are constantly changing. A primary goal of this study is to use empirical evidence to provide a more accurate assessment of uncertainty in LIBS-derived element predictions. We hope to provide practical guidance regarding the angles of ablation and collection that can be tolerated without substantially increasing prediction uncertainty beyond that which already exists under ideal laboratory conditions. Spectra were collected from ten geochemically diverse samples at angles of ablation and collection ranging from 0 degrees to +/- 60 degrees. Ablation and collection angles were changed independently and simultaneously in order to isolate spectral changes caused by differences in ablation angle from those due to differences in collection angle. Most of the variability in atomic and continuum spectra is attributed to changes in the ablation angle, rather than the collection angle. At higher angles, the irradiance of the laser beam is lower and produces smaller, possibly less dense plasmas. Simultaneous changes in the collection angle do not appear to affect the collected spectra, possibly because smaller plasmas are still within the viewing area of the collection optics, even though this area is reduced at higher collection angles. A key observation is that changes in the magnitude of atomic and total emission are <5% and 10%, respectively, in spectra collected with the configuration that most closely resembles field measurements (W) at angles <20 degrees. In addition, variability in atomic and continuum emission is strongly dependent upon sample composition. Denser, more Fe/Mg-rich rocks exhibited much less variability with changes in ablation and collection angles than Si-rich felsic rocks. Elemental compositions of our variable angle data that were predicted using a much larger but conventionally-collected calibration suite show that accuracy generally suffers when the incidence and collection angles are high. Prediction accuracy (for measurements acquired with varying collection and ablation angles) varies from +/- 1.28-1.86 wt% for Al2O3, +/- 1.25-1.66% wt for CaO, +/- 1.90-2.21 wt% for Fe2O3T, +/- 0.76-0.94 wt% for K2O, +/- 2.85-3.61 wt% MgO, +/- 0.15-0.17 wt% for MnO, +/- 0.68-0.78 wt% for Na2O, +/- 0.33-0.42 wt% for TiO2, and +/- 2.94-4.34 wt% SiO2. The ChemCam team is using lab data acquired under normal incidence and collection angles to predict the compositions of Mars targets at varying angles. Thus, the increased errors noted in this study for high incidence angle measurements are likely similar to additional, unacknowledged errors on ChemCam results for non-normal targets analyzed on Mars. Optimal quantitative analysis of LIBS spectra must include some knowledge of the angle of ablation and collection so the approximate increase in uncertainty introduced by a departure from normal angles can be accurately reported. (C) 2017 Elsevier B.V. All rights reserved.

LIBS; Plasma parameter; Quantitative analysis; Qualitative analysis;EMISSION

Laser Induced Breakdown Spectroscopic (LIBS) technique was used to detect calcium and silicon in an unknown sample. In this method plasma was generated by Nd :YAG laser of wavelength 1 064 nm with energy 400 mJ and pulse duration between 5 similar to 10 ns. The method was applied for the qualitative as well as quantitative analysis. In the qualitative analysis, the electron number density (N-e) of plasma containing calcium and silicon is determined showing that N-e of neutral particles is equivalent to 1016 (cm(-3)) whereas for ionized particles it is 10(17) (cm(-3)). Plasma temperature is measured using Boltzmann plot method which must be greater than 10 000 k. Intensity ratio method is used for the quantitative analysis shows various elements in abundance with calcium and silicon in majority.

Laser-induced breakdown spectroscopy; LIBS; in situ K-Ar dating; planetary missions; Mars; geochronology; instrument development; potassium measurements;CHEMCAM INSTRUMENT SUITE; MASS-SPECTROMETRY; MARS; ROCKS; CHRONOLOGY; EVOLUTION; SYSTEM; UNIT

In situ radiogenic isotope measurements to obtain the absolute age of geologic events on planets are of great scientific value. In particular, K-Ar isochrons are useful because of their relatively high technical readiness and high accuracy. Because this isochron method involves spot-by-spot K measurements using laser-induced breakdown spectroscopy (LIBS) and simultaneous Ar measurements with mass spectrometry, LIBS measurements are conducted under a high vacuum condition in which emission intensity decreases significantly. Furthermore, using a laser power used in previous planetary missions is preferable to examine the technical feasibility of this approach. However, there have been few LIBS measurements for K under such conditions. In this study, we measured K contents in rock samples using 30mJ and 15mJ energy lasers under a vacuum condition (10(-3)Pa) to assess the feasibility of in situ K-Ar dating with lasers comparable to those used in NASA's Curiosity and Mars 2020 missions. We obtained various calibration curves for K using internal normalization with the oxygen line at 777nm and continuum emission from the laser-induced plasma. Experimental results indicate that when K2O<1.1wt%, a calibration curve using the intensity of the K emission line at 769nm normalized with that of the oxygen line yields the best results for the 30mJ laser energy, with a detection limit of 88ppm and 20% of error at 2400ppm of K2O. Futhermore, the calibration curve based on the K 769nm line intensity normalized with continuum emission yielded the best result for the 15mJ laser, giving a detection limit of 140ppm and 20% error at 3400ppm K2O. Error assessments using obtained calibration models indicate that a 4 Ga rock with 3000ppm K2O would be measured with 8% (30mJ) and 10% (15mJ) of precision in age when combined with mass spectrometry of Ar-40 with 10% of uncertainty. These results strongly suggest that high precision in situ isochron K-Ar dating is feasible with a laser used in previous and upcoming Mars rover missions.

Baseline removal; Raman spectroscopy; laser-induced breakdown spectroscopy; LIBS; very near; infrared spectroscopy; VNIR;X-RAY-SPECTRA; LEAST-SQUARES; RAMAN-SPECTRA; NMR-SPECTRA; RECOGNITION; SUBTRACTION; REGRESSION; ALGORITHM

The task of proper baseline or continuum removal is common to nearly all types of spectroscopy. Its goal is to remove any portion of a signal that is irrelevant to features of interest while preserving any predictive information. Despite the importance of baseline removal, median or guessed default parameters are commonly employed, often using commercially available software supplied with instruments. Several published baseline removal algorithms have been shown to be useful for particular spectroscopic applications but their generalizability is ambiguous. The new Custom Baseline Removal (Custom BLR) method presented here generalizes the problem of baseline removal by combining operations from previously proposed methods to synthesize new correction algorithms. It creates novel methods for each technique, application, and training set, discovering new algorithms that maximize the predictive accuracy of the resulting spectroscopic models. In most cases, these learned methods either match or improve on the performance of the best alternative. Examples of these advantages are shown for three different scenarios: quantification of components in near-infrared spectra of corn and laser-induced breakdown spectroscopydata of rocks, and classification/matching of minerals using Raman spectroscopy. Software to implement this optimization is available from the authors. By removing subjectivity from this commonly encountered task, Custom BLR is a significant step toward completely automatic and general baseline removal in spectroscopic and other applications.

Laser-induced breakdown spectroscopy; Deep Sea; Double pulse; Cavitation bubble; High pressure;BULK AQUEOUS-SOLUTIONS; ELEMENTAL ANALYSIS; SINGLE-PULSE; SHOCK-WAVES; LIQUIDS; LIBS; EXCITATION; INTENSITY; ABLATION; INSIGHTS

There is a growing interest in the development of sensors use in exploration of the deep ocean. Techniques for the chemical analysis of submerged solids are of special interest, as they show promise for subsea mining applications where a rapid sorting of materials found in the sea bottom would improve efficiency. Laser-Induced Breakdown Spectroscopy (LIBS) has demonstrated potential for this application thanks to its unique capability of providing the atomic composition of submerged solids. Here we present a study on the parameters that affect the spectral response of metallic targets in an oceanic pressure environment. Following laser excitation of the solid, the plasma persistence and the cavitation bubble size are considerably reduced as the hydrostatic pressure increases. These effects are of particular concern in dual pulse excitation as reported here, where a careful choice of the interpulse timing is required. Shadowgraphic images of the plasma demonstrate that cavitation bubbles are formed early after the plasma onset and that the effect of hydrostatic pressure is negligible during the early stage of plasma expansion. Contrarily to what is observed at atmospheric pressure, emission spectra observed at high pressures are characterized by self-absorbed atomic lines on continuum radiation resulting from strong radiative recombination in the electron-rich confined environment. This effect is much less evident with ionic lines due to the much higher energy of the levels involved and ionization energy of ions, as well as to the lower extent of absorption effects occurring in the inner part of the plasma, where ionized species are more abundant. As a result of the smaller shorter-lived cavitation bubble, the LIBS intensity enhancement resulting from dual pulse excitation is reduced when the applied pressure increases. (C) 2017 Elsevier B.V. All rights reserved.

CHEMCAM; MISSION; UNIT

The SuperCam remote sensing instrument suite under development for the National Aeronautics and Space Administration's (NASA) Mars 2020 rover performs laser-induced breakdown spectroscopy (LIBS), remote Raman spectroscopy, visible and infrared (VISIR) reflectance spectroscopy, acoustic sensing, and high-resolution color imaging. The instrument builds on the successful architecture of the ChemCam instrument, which provides LIBS and panchromatic images on the Curiosity rover, adding remote Raman spectroscopy by frequency doubling the laser and using a gated intensified detector to obtain Raman signals at distances to 12 m. To the visible reflectance spectroscopy used by ChemCam, an acousto-optic tunable filter (AOTF)-based IR spectrometer is added to cover the 1.3-2.6 mu m range that contains important mineral signatures. A complementary metal-oxide semiconductor (CMOS) detector provides color (Bayer filter) images at a pixel resolution of 19 mu rad and an optical resolution of 30 mu rad. Sounds are recorded via a Knowles Electret microphone, which is the same one that was included but not used on two earlier missions. The acoustic signals of the LIBS plasmas will provide information on the hardness of the targets, while other sounds (wind, rover sounds) will also be recorded. The laser, telescope, IR spectrometer, and camera reside on the rover's mast and, are provided by the Centre national d'etudes spatiales (CNES), while the LIBS, Raman, and VIS spectrometers and data processing unit are built by Los Alamos National Laboratory (LANL) and reside in the rover body. A calibration target assembly provided by the University of Valladolid, Spain, resides on the back of the rover. The overall mass of the instrument suite is 10.7 kg.

Laser-induced breakdown spectroscopy; LIBS; matrix effects; univariate calibration; minor elements; Cr; Ni; Co; Zn; Mn;GALE CRATER; MARS; SAMPLES

Obtaining quantitative chemical information using laser-induced breakdown spectroscopy is challenging due to the variability in the bulk composition of geological materials. Chemical matrix effects caused by this variability produce changes in the peak area that are not proportional to the changes in minor element concentration. Therefore the use of univariate calibrations to predict trace element concentrations in geological samples is plagued by a high degree of uncertainty. This work evaluated the accuracy of univariate minor element predictions as a function of the composition of the major element matrices of the samples and examined the factors that limit the prediction accuracy of univariate calibrations. Five different sample matrices were doped with 10-85 000 ppm Cr, Mn, Ni, Zn, and Co and then independently measured in 175 mixtures by X-ray fluorescence, inductively coupled plasma atomic emission spectrometry, and laser-induced breakdown spectroscopy, the latter at three different laser energies (1.9, 2.8, and 3.7 mJ). Univariate prediction models for minor element concentrations were created using varying combinations of dopants, matrices, normalization/no normalization, and energy density; the model accuracies were evaluated using root mean square prediction errors and leave-one-out cross-validation. The results showed the superiority of using normalization for predictions of minor elements when the predicted sample and those in the training set had matrices with similar SiO2 contents. Normalization also mitigates differences in spectra arising from laser/sample coupling effects and the use of different energy densities. Prediction of minor elements in matrices that are dissimilar to those in the training set can increase the uncertainty of prediction by an order of magnitude. Overall, the quality of a univariate calibration is primarily determined by the availability of a persistent, measurable peak with a favorable transition probability that has little to no interference from neighboring peaks in the spectra of both the unknown and those used to train it.

BULK AQUEOUS-SOLUTIONS; SINGLE-PULSE; ELEMENTAL ANALYSIS; OPTICAL-BREAKDOWN; OCEANIC PRESSURES; PLASMA FORMATION; WATER; LIQUIDS; NANOSECOND; PARAMETERS

Axial focusing arrangement effects on collinear dual-pulse laser-induced breakdown spectroscopy (DP-LIBS) in a bulk solution were investigated by spectra and fast images. By properly defocusing the second laser pulse beyond the first laser formed bubble (LFB), brighter and larger plasmas could be produced due to higher breakdown efficiency and higher expansion efficiency. It is attributed to a distinct mechanism of underwater DP-LIBS that the plasma mostly forms at the bubble-water interface and then expands into the gaseous LFB. The results show that optimization of the axial focusing arrangement in underwater collinear DP-LIBS enables significant emission enhancements with relatively low laser energies. Published by AIP Publishing.

laser-induced breakdown spectroscopy; ChemCam; Mars Science Laboratory; trace elements; weathering; magmatic differentiation;INDUCED BREAKDOWN SPECTROSCOPY; MARTIAN SOIL COMPONENT; NORTHWEST AFRICA 7034; IN-SITU; INSTRUMENT SUITE; METEORITE; LITHIUM; MINERALOGY; TARGETS; WATER

The Chemistry Camera (ChemCam) instrument onboard Curiosity can detect minor and trace elements such as lithium, strontium, rubidium, and barium. Their abundances can provide some insights about Mars' magmatic history and sedimentary processes. We focus on developing new quantitative models for these elements by using a new laboratory database (more than 400 samples) that displays diverse compositions that are more relevant for Gale crater than the previous ChemCam database. These models are based on univariate calibration curves. For each element, the best model is selected depending on the results obtained by using the ChemCam calibration targets onboard Curiosity. New quantifications of Li, Sr, Rb, and Ba in Gale samples have been obtained for the first 1000 Martian days. Comparing these data in alkaline and magnesian rocks with the felsic and mafic clasts from the Martian meteorite NWA7533from approximately the same geologic periodwe observe a similar behavior: Sr, Rb, and Ba are more concentrated in soluble- and incompatible-element-rich mineral phases (Si, Al, and alkali-rich). Correlations between these trace elements and potassium in materials analyzed by ChemCam reveal a strong affinity with K-bearing phases such as feldspars, K-phyllosilicates, and potentially micas in igneous and sedimentary rocks. However, lithium is found in comparable abundances in alkali-rich and magnesium-rich Gale rocks. This very soluble element can be associated with both alkali and Mg-Fe phases such as pyroxene and feldspar. These observations of Li, Sr, Rb, and Ba mineralogical associations highlight their substitution with potassium and their incompatibility in magmatic melts.

Laser induced breakdown spectroscopy; Remote detection; Partial least squares;

As a kind of spectroscopic technique, the remote laser-induced breakdown spectroscopy (Remote LIBS) can qualitatively or quantitatively measure the elemental compositions of remote targets with high-power laser and focusing optical path. In this work, a Remote LIBS system was designed and established to probe the target from 2 to 10 meters. It is characterized with Cassegrain telescope structure and automatic focusing technique. Based on this system, a method to remotely retrieve the major elemental abundance of rocks is presented. With comparative experiment, the influences on spectral signal by pulse laser energy, acquisition delay time, integration time, accumulative pulse number are analyzed to find out the optimum parameters: the wavelength of laser is 1 064 nm, pulse energy is 120 mJ, delay time is 1. 5 mu s, integration time is 1 ms, and each spectrum data acquired with averaging 30 times detection. 48 pieces of rock specimens and 6 kinds of standard rock samples (shale, granite, andesite, basalt, gneiss and pegmatite) are selected for the experiment. As to the atomic spectra database, 8 characteristic spectral lines of the major elements (Si I 390. 55 nm, Al I 394. 40 nm, Al 1396. 15 nm, Ca II396. 85 nm, Fe I 404. 6 nm, Si I 500. 60nm, Mg I 518. 36nm, Na I 589. 59 nm) were extracted for analyses. Then a PLS model is constructed to quantitatively analyze the rock elements. 48 rock specimens were selected as the training sets to serve the model. The 6 standard samples were used to test the solved model. The testing results shows that the elemental abundance of Si and Al can be predicted accurately with average relative error of only 9. 4% and 9. 6% respectively.