In general, the detection of F and other halogens is challenging through conventional techniques. In this paper, various approaches for the qualitative and quantitative analysis of F using the laser-induced breakdown spectroscopy (LIBS) technique were demonstrated. In LIBS, fluorine detection can be realized by means of atomic lines and molecular bands. For the purposes of our experiment, two sets of pellets with various contents of CaF2, CaCO3 and cellulose were analyzed using a lab-based LIBS system under a He atmosphere. The fluorine atomic line at 685.60 nm was correlated with CaF signals proving their close relationship. Consequently, the limits of detection were determined for both analytical signals. Moreover, conditions necessary for the quantification of F via CaF band signals were estimated. The dependence of the CaF signal on the varying ratio of Ca and F contents was investigated. Finally, a chip of a real CaF2 crystal was prepared and its surface was mapped with Raman and LIBS systems. The obtained elemental and molecular maps showed good numerical correlations. Thus, the yielded results validated the possibility to substitute the fluorine atomic line by non-conventional CaF molecular bands in the qualitative and quantitative LIBS analysis of fluorine.

Multivariate data analysis (MVDA) is getting popular across the spectroscopic community. To assess accurate results, the obtained data should be preprocessed prior to utilization of any MVDA algorithm. The process of data normalization or “internal standardization” is widely used across a broad range of applications. In this manuscript we investigate the utilization of Laser-Induced Breakdown Spectroscopy (LIBS) coupled with MVDA. However, many articles regarding the use of MVDA on data from LIBS do not provide any information about the data pretreatment. This work describes the impact of LIBS data normalization approaches on MVDA classification accuracy. Also, the impact of classical data preprocessing (mean centering and scaling) exploiting the prior utilization of MVDA was studied. This issue was investigated exploiting simple soft independent modelling of class analogies algorithm. The findings were generalized for three sample matrices (steel, Al alloys, and sedimentary ores). Furthermore, the selection of an appropriate normalization algorithm is not trivial since the spectrum of each sample matrix is composed of a different number of elements and corresponding elemental lines.

Laser-Induced Breakdown Spectroscopy; Uranium ore; Elements distribution; Self-organizing maps;

This paper presents a novel approach for processing the spectral information obtained from high-resolution elemental mapping performed by means of Laser-Induced Breakdown Spectroscopy. The proposed methodology is aimed at the description of possible elemental associations within a heterogeneous sample. High-resolution elemental mapping provides a large number of measurements. Moreover, typical laser-induced plasma spectrum consists of several thousands of spectral variables. Analysis of heterogeneous samples, where valuable information is hidden in a limited fraction of sample mass, requires special treatment. The sample under study is a sandstone-hosted uranium ore that shows irregular distribution of ore elements such as zirconium, titanium, uranium and niobium. Presented processing methodology shows the way to reduce the dimensionality of data and retain the spectral information by utilizing self-organizing maps (SOM). The spectral information from SOM is processed further to detect either simultaneous or isolated presence of elements. Conclusions suggested by SOM are in good agreement with geological studies of mineralization phases performed at the deposit. Even deeper investigation of the SOM results enables discrimination of interesting measurements and reveals new possibilities in the visualization of chemical mapping information. Suggested approach improves the description of elemental associations in mineral phases, which is crucial for the mining industry.

Laser-Induced Breakdown Spectroscopy; ;

In this work, we proposed a new data acquisition approach that significantly improves the repetition rates of Laser-Induced Breakdown Spectroscopy (LIBS) experiments, where high-end echelle spectrometers and intensified detectors are commonly used. The moderate repetition rates of recent LIBS systems are caused by the utilization of intensified detectors and their slow full frame (i.e. echellogram) readout speeds with consequent necessity for echellogram-to-1D spectrum conversion (intensity vs. wavelength). Therefore, we investigated a new methodology where only the most effective pixels of the echellogram were selected and directly used in the LIBS experiments. Such data processing resulted in significant variable down-selection (more than four orders of magnitude). Samples of 50 sedimentary ores samples (distributed in 13 ore types) were analyzed by LIBS system and then classified by linear and non-linear Multivariate Data Analysis algorithms. The utilization of selected pixels from an echellogram yielded increased classification accuracy compared to the utilization of common 1D spectra.

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; Lanthanides; Quantitative analysis;RARE-EARTH-ELEMENTS; PLASMA-MASS SPECTROMETRY; NEUTRON-ACTIVATION ANALYSIS; QUANTITATIVE-ANALYSIS; AQUEOUS-SOLUTION; LIBS LIMIT; WASTE SALT; SAMPLES; OXIDE; WATER

Quantitative analysis of Pr, Nd, Ce, La and Sm were carried out simultaneously in LiF-KCl matrix using laser induced breakdown spectroscopic technique. Two non-interfering analytical emission lines have been identified for each lanthanide and using the internal standard method, the calibration curve is constructed from 0.3 to 5% for Pr, Nd, Ce and La and from 0.3 to 3% for Sm. Both the emission lines showed good regression coefficient ) ranging from 0.9953 to 0.9996. The analytical capability of this method is studied through the correlation uncertainty of measured values with its known value in synthetic samples containing all the lanthanides in equal amount . Low value of correlation uncertainty confirms that LIBS has a great potential for quantitative analysis of lanthanides in LiF-KCl matrix.

RARE-EARTH-ELEMENTS; COLLOIDS; LIQUIDS

In this paper, we report the use of laser induced breakdown spectroscopy (LIBS) to detect dissolved Eu and Yb in bulk aqueous solutions. Ten strong emission lines of Eu and one strong emission line of Yb were identified in the underwater LIBS spectra obtained by using Czerny-Turner spectrometer within the wavelength range of 375-515 nm, Temporal evolution of plasma and the effect of laser pulse energy on the spectral emission were studied. Calibration curves using the concentration range from 500 to 10,000 ppm were developed and limits of detection for Eu and Yb were estimated to be 209 and 156 ppm, respectively. (C) 2017 Elsevier B.V. All rights reserved.

Libs; Lithium; Forsterite; Real-time analysis;

A factor of lithium distribution between single-crystal forsterite (Cai:Mg2SiO4) and its melt are studied by laser-induced breakdown spectroscopy. Lithium content in the crystalline phase is found to achieve a saturation at relatively low Li concentration in the melt (about 0.02%wt.). An algorithm and software are developed for real-time analysis of the studied spectra of lithium trace amounts at wide variation of the plasma radiation intensity. The analyzed plasma spectra processing method is based on the calculation of lithium emission part in the total emission of the target plasma for each recorded spectrum followed by the error estimation for the series of measurements in the normal distribution approximation. (C) 2017 Elsevier B.V. All rights reserved.

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.

Laser-induced breakdown spectroscopy; X-ray fluorescence; Reflectance spectroscopy; Data fusion; Mineral interpretation; Partial least squares;INDUCED BREAKDOWN SPECTROSCOPY; QUANTITATIVE MINERALOGY; RAMAN-SPECTROSCOPY; WESTERN-AUSTRALIA; WAVELENGTH; DEPOSIT

This article is extension of the earlier work (Khajehzadeh et al., 2016), where quantitative mineralogical information of slurry samples was achieved using an on-stream LIES analyzer. Despite the great advances in the analytical methods and laser-based measurement techniques, the industrial developers are still demanding novel ideas enabling differentiation between minerals having similar elemental contents such as hematite and magnetite or silicon-bearing minerals such as quartz and other mixed silica minerals since they have different flotation properties. The available analytical techniques for LIES spectral analysis (including the earlier work of this research) could not distinguish between such minerals with identical elemental contents. This work at first presents data fusion of LIES and reflectance spectroscopy and then discusses the data fusion of reflectance spectroscopy and X-ray fluorescence (XRF) measurement techniques operating on the same slurry samples. The results will show that such data integrations enable on-stream and quantitative identification of slurry mineral contents specially for hematite, magnetite, quartz and ferrorichterite which are important minerals in iron ore beneficiation.

CHEMICAL-ANALYSIS; PULSE; PLASMA; PRESSURES; SEAWATER; WATER

The exploitation and research of deep-sea hydrothermal vent has been an issue of great interest in ocean research in recent years. Laser-induced breakdownspectroscopy (LIBS) has great potential for ocean application due to the capabilities of stand-off, multiphase, and multielement analysis. In this work, a newly developed compact 4000 m rated LIBS system (LIBSea) is introduced with preliminary results of sea trials. The underwater system consists of an Nd:YAG single-pulsed laser operating at 1064 nm, an optical fiber spectrometer, an optics module, and an electronic controller module. The whole system is housed in an L800 mm x Phi 258 mm pressure housing with an optical window on the end cap. It was deployed on the remote operated vehicle Faxian on the research vessel Kexue, and in June 2015 was successfully applied for hydrothermal field measurements at the Manus area. The obtained results are shown that the LIBS system is capable of detecting elements Li, Na, K, Ca, and Mg in the hydrothermal area. Profiles of LIBS signals of elements K and Ca have also been obtained during the sea trial. The results show that the K emission line is gradually broadened with depth from sea surface to sea floor (1800 m or so); the K intensity shows a hump shape with maximum value at about 1050 m. The Ca emission line is rapidly broadened below 400 m and slowly narrowed to the sea floor; the Ca intensity shows no obvious change below 400 m and increases continuously to sea floor. A very interesting finding is that the small fluctuations of intensity profile curve of Ca show a degree of correlation with seawater temperature change. The sea trial results prove the performance of LIBSea. After further optimization, it is hoped to apply the LIBS system to the in situ mineral deposits and hydrothermal vent fluid detection in deep sea. (C) 2017 Optical Society of America

Laser-induced breakdown spectroscopy (LIBS); Gold ore; Gold; Silver; Conditional analysis;INSTRUMENTAL NEUTRON-ACTIVATION; RAY-FLUORESCENCE ANALYSIS; LA-ICP-MS; INDUCED PLASMA; QUANTITATIVE-ANALYSIS; PRECIOUS METALS; SULFIDE ORES; SPECTROMETRY; ABLATION; PYRITE

The performance of laser-induced breakdown spectroscopy (LIBS) to identify and quantify gold and silver in ore samples was evaluated. Ores from a gold-producing mine and samples artificially doped with Au and Ag solutions to previously defined concentrations (surrogates) were prepared as 50-mm pellets prior to LIBS analysis. Silver detection and intensity measurement was straightforward for concentrations from 0.4 to 43 mu g/g and from 1.1 to 375 mu/g in ore and surrogate samples, respectively. Au emission lines were not found after ensemble averageor accumulation of 100-single shot LIBS spectra of ore samples containing up to 9.5 mu/g Au. However, the Au signal was present in the spectra of surrogate samples, for which a detection limit of about 0.8 mu g/g was determined. When the number of sampling shots in ore samples increased, various single shot spectra registered Au emission lines. The number of spectra containing Au emission lines increased with the number of single shots. Those results, as well as scanning electron microscopy analysis of ore samples, suggest that the discrete analyte distribution as well as the inherent discrete characteristics associated to LIBS made the presence of gold in the LIBS spark an unlikely occurrence. The particle sampling rates (the percentage of laser pulses expected to sample at least one particle) were estimated for gold concentrations of 1.1 and 10.0 mu/g as 0.04% and 0.32%, respectively. A Monte Carlo simulation indicated that >100 gold-containing particles should be sampled to accurately represent the discrete character of gold in the ore. Sampling 100 such particles requires >10(5) laser pulses over a single pellet. Despite the fact that this rather large number of shots makes difficult to conduct conditional analysis on pellets, for some samples that withstood 5000 shots, gold quantification in ores was successfully achieved at concentrations as low as 1 mu/g. Results are encouraging and illustrate the applicability of LIBS to gold and silver in field semi-quantitative analysis. (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.

spectroscopy; salt efflorescence; rock art; conservation science;RAMAN-SPECTROSCOPY; CULTURAL-HERITAGE; PAINTINGS; DIAGNOSIS; STONE; WALLS; FTIR

Toca Exu do Jurubeba is part of a set of archaeological sites located in the Serra da Capivara National Park (Piaui, Brazil), a region of great world interest due to its archaeological potential, especially rock art. However, rock art is constantly threatened by both natural and anthropic factors. Among the natural salts efflorescences that are deposited on the painted graphics often even concealing them. The present study consisted of the spectroscopic analysis of different saline efflorescence samples of the Serra da Capivara National Park, using examination techniques (optical microscopy and Scanning Electron Microscopy) and analysis (Fourier Transform Infrared and Laser Induced Breakdown Spectroscopy). The analysis allowed to identify at least four different compositions of the samples as a mixture of hydrated calcium oxalate (CaC2O4 H2O) with kaolinite (Al2SiO3(OH)(4)), gypsum (CaSO4 2H(2)O), tetrahydrate calcium nitrate (Ca(NO3)(2) 4H(2)O) and aluminosilicates in the state of fossilization. The obtained results open the way for the conservation of rock art, initially in the archaeological site under study and can serve as basis for other interventions that may be developed in the region.

laser-induced breakdown spectroscopy; soil; magnesium; nonlinear multivariate calibration;RARE-EARTH-ELEMENTS; SAMPLES; LIBS; QUANTIFICATION; DIAGNOSIS; METALS

Laser-induced breakdown spectroscopy (LIBS) coupled with the nonlinear multivariate regression method was applied to analyze magnesium (Mg) contents in soil. The plasma was generated using a 100 mJ Nd:YAG pulsed laser, and the spectra were acquired using a multi-channel spectrometer integrated with a CCD detector. The line at 383.8 nm was selected as the analysis line for Mg. The calibration model between the intensity of characteristic line and the concentration of Mg was constructed. The traditional calibration curve showed that the concentration of Mg was not only related to the line intensity of itself, but also to other elements in soil. The intensity of characteristic lines for Mg (Mg I 383.8 nm), manganese (Mn) (Mn I 403.1 nm), and iron (Fe) (Fe I 407.2 nm) were used as input data for nonlinear multivariate calculation. According to the results of nonlinear regression, the ternary nonlinear regression was the most appropriate of the studied models. A good agreement was observed between the actual concentration provided by inductively coupled plasma mass spectrometry (ICP-MS) and the predicted value obtained using the nonlinear multivariate regression model. The correlation coefficient between predicted concentration and the measured value was 0.987, while the root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) were reduced to 0.017% and 0.014%, respectively. The ratio of the standard deviation of the validation to the RMSEP increased to 8.79, and the relative error was below 1.21% for nine validation samples. This indicated that the multivariate model can obtain better predicted accuracy than the calibration curve. These results also suggest that the LIBS technique is a powerful tool for analyzing the micro-nutrient elements in soil by selecting calibration and validation samples with similar matrix composition.

Laser-induced breakdown spectroscopy; Vector space model; Geological cutting; Identification;SAMPLES

Vector Space Model (VSM) was originally used in document retrieval. It is characterized by extracting the texts from the document and converting the document into a text vector space. VSM compares the similarity between document text vectors and text retrieval text vectors. The document retrieval is accomplished according to the similarity based on the nearest template principle of template matching in pattern recognition. This article applied such principle into the identification of samples based on the characteristic of LIES spectrum. To create the database of characteristic peaks of training dataset, we obtained the spectra template of all kinds of samples from the training dataset and extracted the wavelength and intensity of peaks from the spectra template. In another hand, to create the database of characteristic peak vectors for all the training samples, we calculated the spectral characteristic peak weight and converted the spectra to peak vector space. The characteristic peak vector of the test data set was obtained by the same way. The cosine value between the characteristic peak vector of test data and every characteristic peak vector in the database were calculated and the maximum cosine was taken as the identification result. Geological cuttings, the research subject, were identified by the VSM in this paper. The result demonstrated that the VSM could rapidly identify the spectra from 4 kinds of geological cuttings' LIES spectral and the correct identification rate was 100% after the spectra of the test dataset were averaged. The proposed LIES spectral identification method based on VSM can be expanded to the identification of other spectral data.

Laser-induced breakdown spectroscopy; SF6 oxygen concentration; Wavelet transform; Partial least square; Quantitative analysis;DISCHARGE

Sulfur hexafluoride (SF6) is widely used in gas-insulated high-voltage equipments due to its excellent insulation and arc extinguishing performance. However, when impurities such as trace water and oxygen are present in SF6, the by-products, which are formed due to equipment faults and partial discharge, can react with these impuriti to form stable sulfur oxyfluorides. The equipment insulation performance can be degraded significantly by those stable sulfur oxyfluorides, causing threat to the safety of the power system. The detection and analysis of the impurities such as water, oxygen and decompositions in SF6 are therefore of great importance. In this paper, laser-induced breakdown spectroscopy is employed to measure trace O in SF6. CaF2 is used as window material to solve the degradation of the excitation energy caused by the corrosion of the window material by SF6 decompositions, to eliminate the pollution problem caused by the reaction between the window material and the breakdown products of SF6 gas, and to reduce the change of plasma state caused by the change of excitation condition. By correcting the spectral baseline with an iterative wavelet transform and suppressing the noise with a wavelet transform with soft thresholding, a limit of detection of 38ppm is achieved from the experimental calibration curve. Furthermore, a quantitative model based on partial least squares (PLS) is developed to achieve better stability and precision.

laser-induced breakdown spectroscopy; real-time chemical analysis; geochemical fingerprinting; stratigraphic correlation; provenance determination; mineral exploration;PARTIAL LEAST-SQUARES; DIAMOND EXPLORATION; GOLD MINERALIZATION; YUKON-TERRITORY; SOLID-SOLUTIONS; TRACE-ELEMENTS; RAPID ANALYSIS; ICP-MS; MINERALS; GARNET

A broad suite of geological materials was studied a using a handheld laser-induced breakdown spectroscopy (LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a chemical fingerprint' of any material - solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis (PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis (PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four examples (carbonate minerals and rocks, the oxide mineral pair columbite-tantalite, the silicate mineral garnet and native gold) how portable, handheld LIBS analysers can be used for real-time chemical analysis under simulated field conditions for element or mineral identification, plus such applications as stratigraphic correlation, provenance determination and natural resource exploration.

laser-induced breakdown spectroscopy; borate fusion; bauxite; sample preparation; matrix-match; pellet;PLASMA-MASS SPECTROMETRY; ELEMENTAL ANALYSES; LIBS; SAMPLES; GEOCHEMISTRY; FUSION

Due to matrix interference and sample particle size effects, some of the most important and difficult issues in laser-induced breakdown spectroscopy (LIBS) analysis are the calibration and quantitative measurement of a complex matrix. This study proposes the use of borate fusion as an alternative sample preparation procedure for the quantitative measurement of Al, Fe, Si and Ti in bauxite by LIBS. Analytical calibration curves were made using bauxite certified reference materials (CRM), and the precision and accuracy of the methods were evaluated by analysing an additional bauxite CRM, using two different approaches: pressed powder pellets and fused glass beads. The borate fusion method was the most suitable sample preparation technique, since particle size effects and matrix interference could be minimised, obtaining better linearity on the analytical calibration curves (r(2)), and more accurate and more precise results for bauxite analysis.

WATER-BASED LIQUIDS; METALLIC TRACES; LIBS EMISSION; ENHANCEMENT; IMPROVEMENT; CONFINEMENT; SENSITIVITY; PULSE; LONG

Laser-induced breakdown spectroscopy (LIBS) can benefit from sustaining laser generated plasma with microwaves to enhance elemental detection sensitivity. To achieve efficient microwave coupling, critical factors, such as the electromagnetic environment and reflection coefficient of the coupling device, need to be considered to quantitatively predict the electric-field strength in the plasma location. 3D full-wave electromagnetic simulations were used to design near-field microwave applicators suitable to maximize microwave coupling into the short-lived laser-induced plasmas. The simulations pointed out to four effective and practical designs containing varieties of isolation techniques. The four developed microwave applicators were then used to improve the detection of copper present in a mineral ore solid sample, using LIBS and imaging techniques simultaneously. It was found that, with 1.2 kW microwave power, an applicator design with a 30 mm diameter ground plane can significantly boost the signal of copper line 324.754 nm with a factor of 849, which is, to the authors' best knowledge, the highest reported value. Furthermore, an outstanding signal to noise ratio of 166 was recorded in a solid sample containing a certified 3.38 mg g(-1) copper concentration.

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.

MATRIX CONVERSION; QUANTITATIVE-ANALYSIS; AQUEOUS-SOLUTIONS; METAL DETECTION; HEAVY-METALS; SPECTROMETRY; LIBS; MICROEXTRACTION; PLASMA; MEMBRANE

Laser-induced breakdown spectroscopy (LIBS) is a simple, fast, and direct technique for the elemental analysis of various samples. However, the practical application of this method in direct liquid analysis is limited due to its inherent disadvantages including surface ripples and extinction of emitted intensity. Applicable treatments of liquids always involve complicated procedures or additional instruments, which is disadvantageous to its analytical performance. In this study, we proposed a novel method for the LIBS analysis of liquid samples via a hydrogel-based solidification technique. In this new method, aqueous solution is directly poured into sodium polyacrylate resins. Owing to the high hydroscopicity of sodium polyacrylate resins, the resins quickly form a hydrogel and immediately solidify the liquid samples. After this, the LIBS analysis is directly performed. To estimate the analytical performance of this proposed method, calibration curves were established and limits of detection for Al, Cu, and Cr were obtained. The limits of detection (CODs) for the emission lines of Al(I) 308.21 nm, Cu(I) 324.75 nm, and Cr(I) 425.43 nm were 0.460 mu g mL(-1), 4.69 mu g mL(-1), and 4.44 mu g mL(-1), respectively. According to the obtained results, this proposed method demonstrates its better analytical performance in terms of CODs at the ppm level and requires shorter processing time as compared to other analytical methods based on the LIBS technique for liquid sample analysis. Especially, the short pretreatment of samples and simple auxiliary equipment make this hydrogel-based solidification method bring LIBS out of the laboratory for the direct analysis of environmental liquid samples. The feasibility and potential of this novel method have also been discussed for special analytical applications in slurry samples.

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.

MULTIVARIATE-ANALYSIS; TRACE-METALS; CLASSIFICATION; POLLUTION; CHEMOMETRICS; COMBINATION; DIGESTION; SAMPLES

Laser-induced breakdown spectroscopy (LIBS) is an emerging, multi-elemental and green technique, particularly suitable for the direct analysis of solid samples. In this study, thirty-two superficial sediments collected from Cienfuegos Bay in 2011-2013 were analyzed by LIBS without requiring sample digestion. Al, Ca, Fe, K, Mg, Mn, Na and Ti emission lines were detected in all samples. The full LIBS spectra of the samples were subjected to principal component analysis (PCA) and hierarchical cluster analysis (HCA). Most samples showed a similar emission signal pattern, whereas two samples collected in 2012 and another two in 2013 showed anomalously higher emission signals for Na, Mg and Ca, Mg, respectively. In three of the sediments, the impact of external factors on the ecosystem is the presumable cause of the observed anomalies. The combination of LIBS with multivariate data analysis demonstrated a high capacity for the fast detection of anomalous metal compositions in marine sediments.

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.

Raman; laser-induced breakdown spectroscopy; LIBS; matrix effect; geological samples;QUANTITATIVE-ANALYSIS; SPECTROMETER; MIXTURES

Quantitative Raman analysis was carried out with geologically mixed samples that have various matrices. In order to compensate the matrix effect in Raman shift, laser-induced breakdown spectroscopy (LIBS) analysis was performed. Raman spectroscopy revealed the geological materials contained in the mixed samples. However, the analysis of a mixture containing different matrices was inaccurate due to the weak signal of the Raman shift, interference, and the strong matrix effect. On the other hand, the LIBS quantitative analysis of atomic carbon and calcium in mixed samples showed high accuracy. In the case of the calcite and gypsum mixture, the coefficient of determination of atomic carbon using LIBS was 0.99, while the signal using Raman was less than 0.9. Therefore, the geological composition of the mixed samples is first obtained using Raman and the LIBS-based quantitative analysis is then applied to the Raman outcome in order to construct highly accurate univariate calibration curves. The study also focuses on a method to overcome matrix effects through the two complementary spectroscopic techniques of Raman spectroscopy and LIBS.

Laser-induced breakdown spectroscopy; ChemCam; Hydrogen; Water; Hydration;CHEMCAM INSTRUMENT SUITE; GALE CRATER; OMEGA/MARS EXPRESS; CURIOSITY; HYDROGEN; CALIBRATION; ROVER; MINERALS; CHLORINE; REGOLITH

Laser induced breakdown spectroscopy (LIBS), as performed by the ChemCam instrument, provides a new technique to measure hydrogen at the surface of Mars. Using a laboratory replica of the LIBS instrument onboard the Curiosity rover, different types of hydrated samples (basalts, calcium and magnesium sulfates, opals and apatites) covering a range of targets observed on Mars have been characterized and analyzed. A number of factors related to laserparameters, atmospheric conditions and differences in targets properties can affect the standoff LIBS signal, and in particular the hydrogen emission peak. Dedicated laboratory tests were run to identify a normalization of the hydrogen signal which could best compensate for these effects and enable the application of the laboratory calibration to Mars data. We check that the hydrogen signal increases linearly with water content; and normalization of the hydrogen emission peak using to oxygen and carbon emission peaks (related to the breakdown of atmospheric carbon dioxide) constitutes a robust approach. Moreover, the calibration curve obtained is relatively independent of the samples types. (C) 2017 Elsevier B.V. All rights reserved.

PLASMA-MASS SPECTROMETRY; ICP-MS; EMISSION-SPECTROMETRY; PRECONCENTRATION; SAMPLES; ROCKS; SOIL; CHROMATOGRAPHY; SEPARATION; THORIUM

Univariate and multivariate analyses of six rare earth elements [cerium (Ce), europium (Eu), gadolinium (Gd), neodymium (Nd), samarium (Sm), and yttrium (Y)] have been performed using data from laser-induced breakdown spectroscopy (LIBS). Binary mixtures of oxide forms of each rare earth element in an Al2O3 matrix with their concentrations varying from 1% to 10% by weight in powder form were used as working samples for univariate analysis. For multivariate analysis, complex mixtures of oxides of all these six rare earth elements and Al2O3 in powder form, where the concentration of each element oxide was varied from 1% to 50% by weight one by one, were used to record LIBS spectra. Optimum values of gate delay, gate width, and laser energy were used to get spectra from these samples and spectra were used to develop calibration models. The limits of detection for Ce, Eu, Gd, Nd, Sm, and Y were calculated to be 0.098%, 0.052%, 0.077%, 0.047%, 0.250%, and 0.036%, respectively, from the calibration curves. (C) 2017 Optical Society of America

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; plasma temperature; electron density; limit of detection;ND-YAG LASER; EMISSION

The plasma is generated by focusing a long-pulse (80 mu s) Nd:YAG laser on chromium-doped soil samples. The calibration curves are drawn using the intensity ratio of the chromium spectral line at 425.435 nm with the iron spectral line (425.079 nm) as reference. The regression coefficient of the calibration curve is 0.993, and the limit of detection is 16 mg/kg, which is 19% less than that for the case of a Q-switched laser In the method of long-pulse laser-inducedbreakdown spectroscopy, the laser-induced plasma had a temperature of 15795.907 K and an electron density of 2.988 x 10(17) cm(-3), which exceeded the corresponding plasma parameters of the Q-switched laser-induced breakdown spectroscopy by 75% and 24% respectively.

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.

ACCURACY IMPROVEMENT; WAVELET TRANSFORM; LIBS; SPECTROMETRY; PEAKS

The complex and serious spectral interference makes it difficult to detect trace elements in soil using laser induced breakdown spectroscopy (LIBS). To address it, LIBS-assisted by laser-induced fluorescence (LIES-LIP) was applied to selectively enhance the spectral intensities of the interfered lines. Utilizing this selective enhancement effect, all the interference lines could be eliminated. As an example, the Pb I 405.78 nm line was enhanced selectively. The results showed that the determination coefficient (R-2) of calibration curve (Pb concentration range = 14-94 ppm), the relative standard deviation (RSD) of spectral intensities, and the limit of detection (LOD) for Pb element were improved from 0.6235 to 0.9802, 10.18% to 4.77%, and 24 ppm to 0.6 ppm using LIBS-LIF, respectively. These demonstrate that LIBS-LIF can eliminate spectral interference effectively and improve the ability of LIBS to detect trace heavy metals in soil.

Laser-induced breakdown spectroscopy; Orthogonal dual-pulse; Spectral enhancement; Signal-to-background ratio; Plasma temperature; Electron density;OPTICAL-EMISSION; ENHANCEMENT

In order to improve the detection sensitivity and spectral characteristic of laser-induced breakdown spectroscopy (LIES), re-heating orthogonal dual-pulse configuration is adopted to analyze Fe, Pb, Ca and Mg contained in the sample and soil sample contained different concentrations of heavy mental Cr. Variation relationship between spectral intensity, signal-to-background(SBR) of four characteristic spectral lines Fe I : 404. 581 nm, Pb I : 405. 78 nm, Ca I 422. 67 rim and Mg I : 518. 361 nm and time interval of two laser pulses is discussed, the best time interval of two laser pulses is obtained 1. 0 s. In the condition of single pulse and dual-pulse, the enhancement factor of spectral intensity of four characteristic spectral lines Fe I : 404. 581 nm, Pb I : 405. 78 nm, Ca I : 422. 67 nm and Mg I : 518. 361 nm is respectively 2. 23, 2. 31, 2. 42 and 2. 10; The time evolution characteristic of spectral intensity of characteristic spectral lines Fe I : 404. 581 nm and Ca I : 422. 67 rim is considered, and also the variation relationship between spectral acquisition delay time and SBR of-four characteristic spectral lines, dual-pulse can prolong decay time of spectral intensity and improve the SBR of characteristic spectral lines; time evolution characteristic of plasma temperature and electron density is compared in the condition of single pulse and dual-pulse, maximum elevation of plasma temperature is found to be 730 K, and the maximum increase of electron density is 1. 8 X 10(16) cm(-3). The limits of detection of heavy mental Cr are obtained 38 and 20 mu g center dot g(-1) respectively in condition of single and double pulse, limit of detection of Cr is reduced approximately 2 times by the condition of re-heating orthogonal dual pulse. Results above indicate that reheating orthogonal dual-pulse can improve detection sensibility and spectral characteristic of LIBS technique, which provides an effective method for decreasing the limit of detection of elements.

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.

NMR; LIBS; Surface relaxivity; Paramagnetic impurities; Porous media;NUCLEAR MAGNETIC-RELAXATION; POROUS-MEDIA WETTABILITY; TO-VOLUME RATIO; SEDIMENTARY-ROCKS; NMR RELAXOMETRY; PROTON NMR; PORE SIZES; DIFFUSION; VALIDATION; REGRESSION

Nuclear magnetic resonance (NMR) relaxometry is a common technique used to assess the pore size of fluid-filled porous materials in a wide variety of fields. However, the NMR signal itself only provides a relative distribution of pore size. To calculate an absolute pore size distribution from the NMR data, the material's surface relaxivity needs to be known. Here, a method is presented using laser-induced breakdown spectroscopy (LIBS) to evaluate surface relaxivity in sandstones. NMR transverse and longitudinal relaxation was measured on a set of sandstone samples and the surface relaxivity was calculated from the pore size distribution determined with MICP measurements. Using multivariate analysis, it was determined that the LIBS data can predict with good accuracy the longitudinal (R-2 similar to 0.84) and transverse (R-2 similar to 0.79) surface relaxivity. Analysis of the regression coefficients shows significant influence from several elements. Some of these are elements previously established to have an effect on surface relaxivity, such as iron and manganese, while others are not commonly associated with surface relaxivity, such as cobalt and titanium. Furthermore, LIBS provides advantages compared to current methods to calibrate surface relaxivity in terms of speed, portability, and sample size requirements. While this paper focuses on geological samples, the method could potentially be expanded to other types of porous materials. (C) 2016 Elsevier Inc. All rights reserved.

Stand-off LIBS; heavy metals; environmental samples;INDUCED BREAKDOWN SPECTROSCOPY

Interest in the use of laser-based sensors operating in stand-off mode is increasing due to the wide range of options offered in the evaluation of distant targets. In this work, a stand-off laser induced breakdown spectroscopy (ST-LIBS) system has been developed and demonstrated to determine the heavy elements in soil samples. Initially, different parameters of the device have been optimized in ambient atmosphere and tested for quantitative analysis of Nickel and Chromium at two different stand-off distances (1 m and 6 m). The prepared concentrations were in the range of 100 ppm to 600 ppm. The laser energy of 150 mJ was maintained through out the experiment and to obtain a real time situation the target was in static state.

HELIUM GAS PLASMA; QUANTITATIVE-ANALYSIS; DEUTERIUM

A study of hydrogen and oxygen and its reaction with host elements in a sandstone has been done by laser-induced breakdown spectroscopy (LIBS). The sandstone was irradiated by Nd-YAG laser (1064 nm, 7 ns) with varied energy of 60 mJ till 140 mJ in surrounding air gas pressure of 1 atm and produced plasma. The emission intensities of hydrogen H I 656.2 nm and oxygen O I 777.2 nm in the plasma were captured by HR 2500(+) spectrometer and displayed in intensity as a function of wavelength. The data show that the emission intensities of hydrogen and oxygen increase with increasing laser energy at a gradient of 5.4 and 11.8 respectively every increasing laser energy of 20 mJ. To characterize the reaction process between hydrogen and oxygen with the host elements of the sandstone, a 0.2 ml demineralized water was dropped on the sandstone surface and was analyzed as a function of delay time reaction and temperature. The data show that the oxidation reaction between host elements and oxygen occurred after 25 minutes that the oxygen emission intensity increases and the hydrogen emission intensity decreases. Another data also show that the increasing temperature of sandstone until 80 degrees C increased intermolecular bond between oxygen and host element and dehydrogenation took place after reaching this temperature

INDUCED BREAKDOWN SPECTROSCOPY; SPECTROCHEMICAL ANALYSIS; GEOLOGICAL SAMPLES; ROCKS; OPTIMIZATION; EMISSION; METALS; ORIGIN; PULSES; MARS

We present a study of the plasma generated by transversely excited atmospheric (TEA) CO2 laser irradiation of a basalt sample. The plasma was induced in air at atmospheric pressure. The same sample was also analyzed using a commercial LIBS system based on Nd:YAG laser and time-gated detection. The main plasma parameters, temperature, and electron number density were determined and analytical capabilities of the two systems compared. Despite differences in laser wavelength, pulse duration, applied fluence, and signal detection scheme, the two systems are comparable in terms of element detectability and limits of detection. In both cases, all elements usually present in geological samples were identified. The estimated limits of detection for most elements were below 100 ppm, while for Cu, Cr, and Sr they were around or below 10 ppm. The obtained results led to the conclusion that simple, cost- effective TEA CO2 LIBS system can find applications for geological explorations.

Laser-induced breakdown spectroscopy; miniature laser; nickel ore;QUANTITATIVE-ANALYSIS; INDUCED PLASMA; LIBS; DISCRIMINATION; CONFIGURATION; STEEL; SOIL; CU

A newly designed and developed bench-top instrument is reported for laser-induced breakdown spectroscopy offering compact size and relatively low cost. A miniature laser was designed in the laboratory with a small volume and a light weight. The spectrometer was controlled using laboratory-written software. The instrument is suitable for the direct and rapid analysis of solid samples after simple pretreatment. Good stability and accuracy were achieved for quantitative analysis. The performance of the instrument was evaluated by qualitative and quantitative analyses of nickel ore for Mn, Al, Fe, Cr, Zn, Mg, Si, and Ca. The quantitative analysis showed linear calibration graphs and small relative standard deviations. The results show that the new instrument is suitable for elemental analysis.

laser-induced breakdown spectroscopy; TEA CO2 laser-induced gas plasma; transversely excited atmospheric CO2 laser; powder analysis;INDUCED BREAKDOWN SPECTROSCOPY; SAMPLES; IDENTIFICATION; ABLATION; SOILS

Analysis of powder samples available in small quantities has been carried out using metal-assisted gas plasma by utilizing a transversely excited atmospheric (TEA) CO2 laser. The powder was homogeneously mixed with Si grease, and the mixed powder was painted on a metal subtarget. When a TEA CO2 laserwas directly focused on the metal subtarget at atmospheric pressure of He gas, a high-temperature He gas plasma was induced. It is assumed that the powder particles were vaporized to be effectively atomized and excited in the gas plasma region. This method has been employed in the rapid analyses of elements in organic and inorganic powder samples present in small quantities. Detection of trace elements of Cr and Pb has been successfully made by using the supplement powder and loam soil, respectively. The detection limits of Pb in loam soil were approximately 20 mg/kg.

laser-induced breakdown spectroscopy; principal component analysis; sedimentary rock; metamorphic rock; igneous rock;LIBS

This study deals with the analysis of rocks using laser-induced breakdown spectroscopy (LIBS) coupled with principal component analysis. The spectra of sedimentary, metamorphic, and igneous rock samples were recorded in the 200-900 nm spectral range. The atomic lines of elements such as Si, Ca, Mg, Fe, Na, and K along with lighter elements, namely C, H, N, and O, were observed in these spectra. Multivariate analysis in combination with LIBS was used to classify the samples. For principal component analysis, a 12 x 5849 data matrix was formed using the results of LIBS. The plot of the analysis revealed similarities between the sedimentary and metamorphic rock samples compared with the igneous rock sample. Thus, the present study demonstrates that LIBS coupled with principal component analysis can become an important tool for rapid classification and in-situ discrimination of rock samples.

ADSORPTION; VALIDATION; REGRESSION; SAMPLES; ARGON; SIZE

From healthcare to cosmetics to environmental science, the specific surface area (SSA) of micro- and mesoporous materials or products can greatly affect their chemical and physical properties. SSA results are also widely used to examine source rocks in conventional and unconventional petroleum resource plays. Despite its importance, current methods to measure SSA are often cumbersome, time-consuming, or require cryogenic consumables (e.g, liquid nitrogen). These methods are not amenable to high-throughput environments, have stringent sample preparation requirements, and are not practical for use in the field. We present a new application of laser-induced breakdown spectroscopy for rapid measurement of SSA. This study evaluates geological samples, specifically organic-rich oil shales, but the approach is expected to be applicable to many other types of materials. The method uses optical emission spectroscopy to examine laser-generated plasma and quantify the amount of argon adsorbed to a sample during an inert gas purge. The technique can accommodate a wide range of sample sizes and geometries and has the potential for field use. These advantages for SSA measurement combined with the simultaneous acquisition of composition information make this a promising new approach for characterizing geologic samples and other materials.

II SPECTRAL-LINES; ATOMIC TRANSITION-PROBABILITIES; STARK-BROADENING PARAMETERS; CALIBRATION-FREE; INDUCEDPLASMA; QUANTITATIVE-ANALYSIS; CRITICAL COMPILATION; SELF-ABSORPTION; WIDTHS; SHIFTS

We report a validation experiment of the C sigma-LIBS method, proposed recently by our group for quantitative laser-induced breakdown spectroscopy. This method is applied to determine eight elements (Si, Al, Ca, Mg, Fe, Ti, Mn, and V) in rocks prepared as fused glass samples, having a wide range of certified concentrations. The characterization stage of the method is performed using only two standard fused glass samples prepared from mixtures of pure compounds (SiO2, Al2O3, Fe2O3 and CaCO3). The average precision obtained is 3.4% for concentrations higher than 0.1 wt%. This validation suggests that the accuracy and precision of this technique, if combined with fused glass sample preparation under favourable conditions, may become as good as those produced by certification laboratories.

INDUCED BREAKDOWN SPECTROSCOPY; MOLECULAR-EMISSION; LASER; AIR; SPECTROMETRY; CHLORINE

The determination of fluorine in solid samples using Laser Induced Breakdown Spectroscopy (LIBS) is a challenging task due to the low excitation efficiency of this element. Recently, the use of molecular CaF bands was demonstrated to improve the analytical capabilities of LIBS fluorine detection in Ca-containing samples. In this work, a novel approach has been developed to extend this methodology for fluorine quantification in calcium-free samples. In particular, the on-line nebulization of a Ca-containing solution on the surface of a fluorine containing sample has been successfully evaluated to obtain the desired CaF molecular emission. Nebulization parameters have been optimized in order to maximize the molecular emission. A linear relationship between the CaF molecular emission signal and the amount of F in the solid samples has been obtained. The calculated limit of detection for fluorine (about 50 mu g g(-1)) is in the same order of magnitude as that obtained for Ca-containing samples. This novel approach for fluorine quantification opens new ways for the analysis of halogens in solid samples.

Laser-Induced Breakdown Spectroscopy; Uranium; principal component analysis; Chemical mapping; Sandstone-hosted deposit; X-ray Fluorescence;

The goal of this work is to provide high resolution mapping of uranium in sandstone-hosted uranium ores using Laser-Induced Breakdown Spectroscopy (LIBS) technique. In order to obtain chemical image with highest possible spatial resolution, LIBS system in orthogonal double pulse (DP LIBS) arrangement was employed. Owing to this experimental arrangement the spot size of 50 μm in diameter resulting in lateral resolution of 100 μm was reached. Despite the increase in signal intensity in DP LIBS modification, the detection of uranium is challenging. The main cause is the high density of uranium spectral lines, which together with broadening of LIBS spectral lines overreaches the resolution of commonly used spectrometers. It results in increased overall background radiation with only few distinguishable uranium lines. Three different approaches in the LIBS data treatment for the uranium detection were utilized: i) spectral line intensity, ii) region of apparent background and iii) multivariate data analysis. By utilizing multivariate statistical methods, a specific specimen features (in our case uranium content) were revealed by processing complete spectral information obtained from broadband echelle spectrograph. Our results are in a good agreement with conventional approaches such as line fitting and show new possibilities of processing spectral data in mapping. As a reference technique to LIBS was employed X-ray Fluorescence (XRF). The XRF chemical images used in this paper have lower resolution (approximately 1–2 mm per image point), nevertheless the elemental distribution is apparent and corresponds to presented LIBS experiments.

Laser-Induced Breakdown Spectroscopy; Multivariate classification; Echelle spectrometer; Czerny-Turner spectrometer;

The objective of this work was to assess a part of echelle Laser-Induced Plasma spectra (ranging from 200 to 1000 nm) that could be most effectively employed for rocks classification. Therefore, a 60 nm wide spectral window mask was iteratively moved over the broadband echelle spectra. Each created narrow artificial spectral windows (60 nm) was used for the classification of rock samples using various Multivariate Data Analysis (MVDA) algorithms, reaching more than 99% of the overall accuracy in certain cases. Afterwards, the Czerny-Turner spectrometer (having higher sensitivity compared to the echelle spectrometer) was aligned to the a priori selected and the most effective spectral regions and rocks samples were re-measured. Consequently the MVDA analyses were utilized again, providing also satisfying classification results yielding more than 99% of the overall accuracy. Measurements of 28 sedimentary ores (certified reference materials) were done utilizing commercially available X-Trace device (AtomTrace), where spectrometers in both configurations (echelle and Czerny-Turner) were exploited.