Multi-elemental analysis of solidified mineral melt samples by Laser-Induced Breakdown Spectroscopy coupled with a linear multivariate calibration

Laser-Induced Breakdown Spectroscopy (LIBS) has been successfully applied for multi-elemental analysis of solidified mineral melt samples containing several oxides present in various concentrations. The plasma was generated using a Nd:YAG laser and the spectra were acquired using an Echelle spectrometer, coupled to an ICCD detector, which covers a spectral range from 200 to 780 nm. Using a set of 19 calibration samples, we first established univariate calibration curves for the major elements (Al, Fe, Mg, Ca, Ti and Si). We found out that the presence of matrix effects makes such a model, traditionally used in LIBS, not satisfying for quantitative analysis of such samples. Indeed, no sufficiently linear trends can be extracted from the calibration curves for the elements of interest considering all the samples. Instead, a much more robust calibration approach was obtained by considering a multivariate model. The matrix effects are then taken into account by correcting the spectroscopic signals emitted by a given species due the presence of the others ones. More specifically, we established here a calibration model using a 2nd order polynomial linear multivariate inverse regression. The capability of this approach was then checked using a 2nd set of samples with an unknown composition. A good agreement was observed between the analysis provided by X-ray fluorescence (XRF) and the LIBS measurements coupled to the multivariate model for the unknown samples.     

Effect of target composition on the emission enhancement observed in Double-Pulse Laser-Induced Breakdown Spectroscopy

The effect of the matrix composition on the emission enhancement observed in Double-Pulse (DP) Laser-Induced Breakdown Spectroscopy (LIBS) was studied for several pure metal targets (Al, Au, Co, Cu, Fe, Mn, Mo, Ni, Pb, Pt, Si and W). The measurements were performed in air by using a dual-pulse Nd:YAG ns laser emitting 60mJ pulses at 1064nm wavelength. The measurement of the emission enhancement for neutral and ionic lines of all the samples showed a wide range of results. Very low enhancement was observed in Pb, Ni and Mn while the highest values of enhancement were obtained in Cu, Al and Au. The space-averaged thermodynamic parameters of the induced plasmas in DP and in SP LIBS were calculated and the enhancement of ablated atomized mass in DP case was spectroscopically estimated in all the targets. A correlation seems to exist between the ablated atomized mass enhancement and the plasma temperature increase in the DP configuration. An attempt was made to correlate the increase of these two quantities with the melting point and heat, boiling point and heat, reflectivity and ionization energy of the metal. No evident correlation was found. At the opposite, a correlation was observed between the ablated atomized mass enhancement and the thermal diffusivity of the metal.     

Analytical optimization of some parameters of a Laser-Induced Breakdown Spectroscopy experiment

Laser-Induced Breakdown Spectroscopy (LIBS) experiments are performed on standard metallic samples, in air at atmospheric pressure, using a Nd:YAG laser at 1064 nm and a fiber located close to the plasma to collect its emission. This configuration is chosen because it is representative of many LIBS setups. The influence of several experimental parameters is studied in order to optimize the analytical performances: signal-to-background ratio (SBR), line intensity and repeatability. Temporal parameters of the detector are adjusted for each measurement to maximize the SBR. The signal is found to linearly depend on the pulse energy over our range of investigation. This behavior is related to the increase of the number of vaporized atoms when the pulse energy increases. Complementary measurements of plasma dimensions support our conclusions. We show the existence of an optimum fluence on the sample that gives the highest signal and the lowest relative standard deviation (RSD), and which does not depend on the pulse energy. Finally we demonstrate that ablation is much more efficient using a laser beam with a high numerical aperture, other experimental parameters being unchanged, because of a less pronounced laser shielding by the plasma. Analytical consequences of this result are discussed.     

Evaluation of self-absorption of manganese emission lines in Laser Induced Breakdown Spectroscopy measurements

This paper is part of a more general study aimed to the determination of the best experimental procedures for reliable quantitative measurements of Fe–Mn alloys by LIBS. In this work, attention is pointed on the self-absorption processes, whose effect deeply influences the LIBS measurements, reflecting in non-linear calibration curves. The effect of self-absorption on the line intensity can be quantified by defining a self-absorption coefficient, that measures the deviation of the line intensity from the linear extrapolation of the curve of growth in the optically thin regime. The authors demonstrated in a previous paper that self-absorption coefficients could be calculated once the electron density of the plasma is known and the Stark coefficients of the lines are available. However, when the Stark coefficients of the lines of interest are not known, a different approach is needed. In this work a new method for evaluation of self-absorption coefficients in LIBS measurements is presented, which does not require the knowledge of Stark coefficients. In order to understand the basic principles and setting out the theoretical tools that will be used for the analysis of the alloys, a preliminary study was done on pure Mn; LIBS spectra were acquired in different experimental conditions, at different laser energies and different delays after the laser irradiation of the sample. Moreover, collinear double pulse measurements were also performed. Analytical relations were derived and experimental procedures devised for evaluation of the self-absorption coefficients of several Mn lines, which are important for characterization and control of the experimental conditions in which the analysis is performed.     

Characterization of cinematographic films by Laser Induced Breakdown Spectroscopy

The emulsion-coated transparent plastic-base film has been the main carrier for production and preservation of motion picture contents since the 19th century. The knowledge of the composition of black and white silver gelatine cinematographic films is of great importance for the characterization of the photographic process and for identifying the optimum conditions for conservation. A cinematographic film is a multi-component system that consists of a layer of photographic emulsion overcoating a polymeric support (plasticized cellulose triacetate) and a protective transparent cross-linked gelatine layer coating the emulsion. In the present work, Laser Induced Breakdown Spectroscopy (LIBS) is used to characterize the composition of the materials of cinematographic films. LIB spectra of film samples and of different individual film components, polymeric support and reference gelatines, were acquired in vacuum by excitation at 266 nm (Q-switched Nd:YAG laser, 6 ns, 10 Hz). In the cinematographic film, silver lines from the light-sensitive silver halide salts of the photographic emulsion are accompanied by iron, lead, chrome and phosphorus lines. Iron and lead are constituents of film developers, chrome is included in the composition of the hardening agents and phosphorus has its origin in the plasticizer used in the polymeric support. By applying successive pulses on the same spot of the film sample, it was possible to observe through stratigraphic analysis the different layers composition. Additionally, the results obtained reveal the analytical capacity of LIBS for the study and classification of the different gelatine types and qualities used for the protecting layer and the photographic emulsion.     

Optimization of micro-Laser Induced Breakdown Spectroscopy analysis and signal processing

As a result of continuing instrumental development (Echelle spectrometer and ICCD detectors), micro-Laser Induced Breakdown Spectroscopy analysis may become an increasingly recognized analytical technique for determining elemental compositions of geologic materials. Best conditions of time resolution conditions (delay and time acquisition window) are estimated with respect to the collection geometry of optical plasma emission of our system. It turns out that the level of the Bremsstrahlung continuum emission is weak in the first tens of nanoseconds after the laser excitation pulse. The enlargement of the emission lines is identified in the first 100 ns but remains comparable to the spectral resolution of our system. Thus, results show that time-resolved conditions are not necessarily required to perform elemental analysis at the micrometric scale using LIBS, contrary to macro-LIBS. This suggests potential improvements of micro-LIBS analysis (sensitivity and spectral resolution) using non-intensified CCD connected with the laser pulse.     

Fast analysis of complex metallic alloys by double-pulse time-integrated Laser-Induced Breakdown Spectroscopy

Results are reported on the application of double-pulse Laser-Induced Breakdown Spectroscopy (LIBS) for fast analysis of complex metallic alloys. The approach followed for the determination of the composition of the alloys is based on the time-integrated acquisition of LIBS spectra emitted by plasmas induced by collinear double-pulse laser excitation. The spectra are analysed using the Partial Least Squares method, which allows the determination of sample composition even in the presence of strong spectral interferences. The results shown indicate the possibility of measuring the composition of complex metallic alloys in very short times and using relatively cheap LIBS instrumentation.     

Online analysis of potassium fertilizers by Laser-Induced Breakdown Spectroscopy

Presently, online analysis in potassium fertilizers industry is performed by Natural Radioactivity Analyzers. Laser Distance Spectrometry (LDS) has tested, by laboratory scale, the possibility of Laser-Induced Breakdown Spectroscopy (LIBS) technique implementation for online fertilizers production control. The main advantage of the system comparing to the existing technique is the principal possibility to analyze all relevant elements, such as K, Na, Mg, and not only K40 isotope as done in natural radiation analytical systems. Good correlations between online LIBS results with chemical analysis data of K, Na and Mg impurities of samples from Russia, Belarus and Israel demonstrate that LIBS system is a perspective tool for online control of those elements in field conditions.     

Analysis of Roman-Hispanic Archaeological Ceramics using Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a useful tool for characterization of archaeological samples because it involves little or no sample preparation, and it allows on-site rapid and nondestructive analysis. In this study, ceramics from the archaeological site of Labitolosa (Huesca) were analyzed qualitatively and quantitatively. Furthermore, a protocol is described for the determination of iron in archaeological materials by interpolating calibration graphs and standard addition. Moreover, the potential of LIBS for direct quantitative analysis of iron in real archaeological materials was evaluated, and optimum analytical conditions were determined. The reproducibility of LIBS spectra from different archaeological samples was investigated as a function of the number of laser shots. The results were compared with those of a reference material.     

Miniaturized Laser-Induced Breakdown Spectroscopy for the in-situ analysis of the Martian surface: Calibration and quantification

We report on our ongoing studies to develop Laser-Induced Breakdown Spectroscopy (LIBS) for planetary surface missions to Mars and other planets and moons, like Jupiter's moon Europa or the Earth's moon. Since instruments for space missions are severely mass restricted, we are developing a light-weight miniaturized close-up LIBS instrument to be installed on a lander or rover for the in-situ geochemical analysis of planetary surface rocks and coarse fines. The total mass of the instrument will be ≈ 1 kg in flight configuration. Here we report on a systematic performance study of a LIBS instrument equipped with a prototype laser of 216 g total mass and an energy of 1.8 mJ. The LIBS measurements with the prototype laser and the comparative measurements with a regular 40 mJ laboratory laser were both performed under Martian atmospheric conditions.     

Strategies for Mars remote Laser-Induced Breakdown Spectroscopy analysis of sulfur in geological samples

The key to understanding the sulfur history on Mars is to identify and determine sulfate and sulfide compositions and then to draw from them geologic clues about their environments of formation. To lay a foundation for use of remote LIBS to sulfur analysis in planetary exploration, we have undertaken a focused study of sulfur LIBS in geological samples in a simulated Mars atmosphere, with experimental parameters replicating the ChemCam LIBS instrument. A suite of twelve samples was selected, including rocks rich in minerals representative of sulfates and sulfides that might be encountered on Mars. Univariate analysis of sulfur emission lines did not provide quantitative information. Partial least squares (PLS) analysis was successful at modeling sulfur concentrations for a subset of samples with similar matrices. Sulfide minerals were identified on the basis of other siderophile or chalcophile peaks, such as those arising from Zn and Cu. Because the S lines are very weak compared to those of other elements, optimal PLS results were obtained by restricting the wavelength range to channels close to the most intense sulfur lines ~ 540-570 nm. Principal components analysis was attempted on the dataset, but did not differentiate the samples into meaningful groups because the sulfur lines are not strong enough. However, areas of the relatively weak S, H, and O peaks may be used to correctly classify all samples. Based on these outcomes, a flowchart that outlines a possible decision tree for identification and quantification of sulfur in remote LIBS analysis was constructed. Results suggest that LIBS data acquired under Mars conditions can meet the science requirements for the ChemCam instrument.     

Laser Induced Breakdown Spectroscopy methodology for the analysis of copper-based-alloys used in ancient artworks

In this paper Laser Induced Breakdown Spectroscopy has been applied for determining the elemental composition of a set of ancient bronze artworks coming from archaeological site of Minervino Murge — Southern of Italy (dated around VII b.C.). Before carrying on the analysis of the archaeological samples, the characterization of the analytical technique has been accomplished by investigating the trueness of the typical assumptions adopted in LIBS, such as Local Thermodynamic Equilibrium, congruent ablation and plasma homogeneity. With this purpose, two different laser pulse durations, 7 ns and 350 fs, have been used. We have focused our attention on LIBS analysis of bronze standards by considering and discussing the bases of both methodology and analytical approach to be followed for the analysis of ancient copper-based-alloy samples. Unexpectedly, regardless from the laser pulse duration, the LIBS technique has shown, by considering an adequate approach on the emitting plasma features, that its peculiarities are anyway preserved so that a fast analysis of ancient copper-based-alloys can be achieved. After verifying the suitability of the methodology, it has been possible to fulfill the typical assumptions considered for the LIBS calibration curves method and use it for ancient bronze artworks analysis.     

Analysis of Pre-Hispanic Archaeological Samples Using Laser-Induced Breakdown Spectroscopy (LIBS)

Abstract

Laser-induced breakdown spectroscopy gave excellent results with respect to reproducibility, sensitivity, nondestructiveness, rapid elemental analisys, and depth-profile analisys. In this work, elements contained in pigments from pre-Hispanic ceramics of Cajamarquilla were identified. Also, some textile samples from the Uquira site, located in Asia Valley between Mala and Cañete (Perú), were analyzed. For this purpose, a Quantel Ultra CFR pulsed Nd/YAG laser was used.     

Study of sub-mJ-excited laser-induced plasma combined with Raman spectroscopy under Mars atmosphere-simulated conditions

Laser-Induced Breakdown Spectroscopy (LIBS) and Raman spectroscopy are complimentary techniques. LIBS yields elemental information while Raman spectroscopy yields molecular information about a sample, and both share similar instrumentation configurations. The combination of LIBS and Raman spectroscopy in a single instrument for planetary surface exploration has been proposed, however challenges exist for developing a combined instrument. We present LIBS and Raman spectroscopy results obtained using a diode pumped, intracavity doubled, Q-switched, Nd:YLF laser operating at 523 nm, which overcomes some of the difficulties associated with a combined instrument. LIBS spectra were obtained with 170 μJ per pulse at 4 Hz repetition rate in a low pressure Mars-simulated atmosphere and Raman spectra produced with 200 mW at 100 kHz. The Nd:YLF laser is switchable between LIBS and Raman spectroscopy modes only by a change in Q-switch repetition rate. Emissions from Ca, Ca II, Fe, Fe II, Mg, Na, and O atom were identified in the μ-LIBS spectrum of oolithic hematite. Evidence was found for a change in plasma dynamics between 7 and 5 Torr that could be explained as a decrease in plasma temperature and electron density below 5 Torr. This is relevant to future Mars exploration using LIBS as the mean surface pressure on Mars varies from 3.75 to 6 Torr. LIBS plasma dynamics should be carefully evaluated at the pressures that will be encountered at the specific Mars landing site.     

Multi-element analysis of iron ore pellets by Laser-induced Breakdown Spectroscopy and Principal Components Regression

Laser-induced Breakdown Spectroscopy (LIBS) in combination with Principal Components Regression (PCR) has been applied to determine the elemental composition of a series of run-of-mine (ROM) iron ore samples. The samples were presented for measurement both as compressed pellets and as loose chipped material. The present paper details the results of the measurements of the compressed pellets. Results from ore chips will be reported separately. LIBS spectral data was recorded in three separate spectral regions to measure major, minor and trace components of the iron ore sample pellets. Background stripping, normalization and spectral cleaning were applied to minimize the relative standard deviations of the LIBS data. PCR analysis was then applied to produce calibration models for iron, aluminum, silicon, manganese, potassium and phosphorous. These calibration models were then validated using independent LIBS measurements. Robust calibration models were determined for iron, aluminum, silicon and potassium, whilst the results for manganese were encouraging. Phosphorous, present at low levels in the ores measured, remained the most difficult element to determine accurately. The combination of LIBS and PCR shows potential for in-situ on-line determination of ore composition.     

A numerical study of expected accuracy and precision in Calibration-Free Laser-Induced Breakdown Spectroscopy in the assumption of ideal analytical plasma

Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) has been proposed several years ago as an approach for quantitative analysis of Laser-Induced Breakdown Spectroscopy spectra. Recently developed refinement of the spectral processing method is described in the present work. Accurate quantitative results have been demonstrated for several metallic alloys. However, the degree of accuracy that can be achieved with Calibration-Free Laser-Induced Breakdown Spectroscopy analysis of generic samples still needs to be thoroughly investigated. The authors have undertaken a systematic study of errors and biasing factors affecting the calculation in the Calibration-Free Laser-Induced Breakdown Spectroscopy spectra processing. These factors may be classified in three main groups: 1) experimental aberrations (intensity fluctuations and inaccuracy in the correction for spectral efficiency of a detection system), 2) inaccuracy in theoretical parameters used for calculations (Stark broadening coefficients and partition functions) and 3) plasma non-ideality (departure from thermal equilibrium, spatial and temporal inhomogeneities, optical thickness, etc.). In this study, the effects of experimental aberrations and accuracy of spectral data were investigated, assuming that the analytical plasma is ideal. Departure of the plasma conditions from ideality will be the object of future work. The current study was based on numerical simulation. Two kinds of metallic alloys, iron-based and aluminum-based, were studied. The relative weight of the error contributions was found to depend on the sample composition. For the here-investigated samples, the experimental aberrations contribute to the overall uncertainty on the quantitative results more than theoretical parameters. The described simulation method can be applied to the Calibration-Free Laser-Induced Breakdown Spectroscopy analysis of any other kind of sample.     

Quantitative Analysis of Roman Archeological Ceramics by Laser-Induced Breakdown Spectroscopy

In recent decades, numerous analytical techniques have been used for the analysis of archeological samples. Laser-induced breakdown spectroscopy (LIBS) is a promising technique due to its practically nondestructive nature and minimal sample preparation. In this work, LIBS was used for the qualitative and quantitative elemental analyses of pottery manufactured in ancient settlements of Rome. The qualitative study showed that the ceramics were composed of Fe, Ca, and Mg. For quantitative analysis, calibration curves of Fe, Ca, and Mg were constructed with reference samples of each element in a KBr matrix with zinc as an internal standard. The results obtained by LIBS were compared with values obtained by atomic absorption.     

激光诱导击穿光谱法分析焊丝样品

采用激光诱导击穿光谱法(LIBS)对焊丝样品中的硅、锰、磷、硫、铬及镍元素进行测定。采用扫描电子显微镜和激光共聚焦显微镜观察了样品经激光脉冲烧蚀后的形貌,并考察了各元素的谱线强度与激光脉冲个数之间的关系,从而确定了预剥蚀激光脉冲个数。通过分析标准样品建立了单个元素的谱线强度与其质量分数之间的标准曲线,相关系数在0.989~0.999之间。本方法对焊丝样品的分析结果与经典的电感耦合等离子体原子发射光谱法和高频红外硫碳分析方法的测定结果相吻合,其精密度稍差于经典的分析方法。     

Archaeometric Analysis of Ancient Copper Artefacts by Laser-Induced Breakdown Spectroscopy Technique

Twelve archaeological copper objects from the burial site of “Fontino” cave, near Grosseto, (around 2500–2000 B.C.) were analysed using laser-induced breakdown spectroscopy. Qualitative results and a preliminary study of the samples’ composition are reported and used to make a quantitative estimate; based on these results, the samples were classified using principal components statistical analysis. The perspectives of using laser-induced breakdown spectroscopy for archaeometric analysis are also discussed.