Laser-induced Breakdown Spectroscopy Analysis Research Articles

Approach to using 3D laser-induced breakdown spectroscopy (LIBS) data to explore the interaction of FLiNaK and FLiBe molten salts with nuclear-grade graphite

3D LIBS analysis provides insight into interaction of molten salts with nuclear grade graphites, including fluorine and other low-Z elements, through principal component and emission correlation analysis, as well as emission mapping/profiling.

An image auxiliary method for laser-induced breakdown spectroscopy analysis of coal particle flow

An image information-assisted spectral screening method was proposed for improving the coal particle flow detection performance via LIBS and its positive effects on spectral stability and quantitative analysis were verified.

Correction of moisture interference in laser-induced breakdown spectroscopy detection of coal by combining neural networks and random spectral attenuation

Increased humidity causes terrible accuracy in laser-induced breakdown spectroscopy analysis of coal. The moisture interference was reduced using artificial neural networks (ANN) combined with random spectral attenuation in this study.

Improving the LIBS analysis of heavy metals in heterogeneous agricultural samples utilizing large laser spotting

Improving the laser-induced breakdown spectroscopy analysis of heterogeneous agricultural samples utilizing large laser spotting.

Quantitative Analysis and Identification Improvement in Laser-Induced Breakdown Spectroscopy by Self-Absorption Correction and Artificial Neural Network

In this research, the laser-induced breakdown spectroscopy (LIBS) technique is used for concentration prediction and identification in aluminum alloys. For this purpose, calibration-free LIBS (CF-LIBS) and artificial neural network (ANN) analyses were implemented. Self-absorption correction (SAC) and gate time improvement in CF-LIBS lead to more accurate quantitative results and concentration calculation close to real values. In addition, in identification of different Al alloys by ANNs, results show that using corrected lines intensity of fundamental species has better results in network construction and fewer errors.

Phosphorous Determination in Biochar-Based Fertilizers by Spark Discharge-Laser-Induced Breakdown Spectroscopy

Biochar-based fertilizers are a new attractive alternative to P supplementation for crops, as they can gradually release the nutrient, avoiding losses and improving soil quality. In this regard, the evaluation of the P amount in biochar-based fertilizers is extremely important for their quality control. Analytical techniques that require sample solubilization are not very efficient for this task, as biochar is difficult to solubilize. Laser-induced breakdown spectroscopy (LIBS) is a promising technique to respond to this demand, as it enables a direct analysis of solid samples, avoiding the complicated process of sample solubilization. In this work, a novel method based on spark discharge (SD) coupled to LIBS was evaluated for P determination in biochar-based fertilizers prepared from three different biomasses. To overcome calibration problems in LIBS analysis, a matrix-matching procedure accomplished by the addition of eucalyptus biochar to calibration standards was used in experiments. This procedure minimized matrix effects and allowed us to achieve a satisfactory accuracy even when applied to similar but different matrices. Furthermore, the developed method is simple, fast, direct, does not generate post-analysis residues and appears appropriate for the quality control of sustainable biochar-based fertilizers and other biochar products.

Laser-induced breakdown spectroscopy analysis of water solutions deposited on PTFE surface: Influence of copper oxide nanoparticles and NELIBS effect

The analytical potential of LIBS for the analysis of liquid solutions was evaluated using two experimental setups, one based on a TEA CO2 laser and the other in which Nd:YAG laser was used. Polytetrafluoroethylene (PTFE) was used as a substrate on which a 10 μL drop of analyte solutions with different concentrations of analyte elements, Be, Cr, Ni, Co, Pb, Tl, and V, were deposited and dried. The samples were deposited either directly on the PTFE or over the pre-deposited layer of copper oxide nanoparticles to study the influence of nanoparticles (NPs) on the ablation and plasma excitation. The obtained results imply that the presence of Cu oxide NPs does not significantly affect the analytical performance of LIBS based on TEA CO2 laser for analysis of solutions. At the same time, it was shown that plasma created by TEA CO2 laser radiation efficiently excited ablated material, making metal elements detectable in the sub-ppm concentration range. On the other hand, Cu oxide NPs significantly influence the formation and the analytical properties of plasma induced by Nd:YAG laser. Without the presence of NPs, the intensities of analyte lines were very low, unsuitable for spectrochemical analysis. At the optimal surface concentration of NPs, 0.36 mg/cm2, the intensity of analyte lines was increased more than ten times. Limits of detection of Be and Cr were 5.3 ppb and 33 ppb, with good linearity of curves of growth.

Rapid Determination and Quantification of Nutritional and Poisonous Metals in Vastly Consumed Ayurvedic Herbal Medicine (Rejuvenator Shilajit) by Humans Using Three Advanced Analytical Techniques.

‏Shilajit is used commonly as Ayurvedic medicine worldwide which is Rasayana herbo-mineral substance and consumed to restore the energetic balance and to prevent diseases like cognitive disorders and Alzheimer. Locally, Shilajit is applied for patients diagnosed with bone fractures. For safety of the patients, the elemental analysis of Shilajit is imperative to evaluate its nutritional quality as well as contamination from heavy metals. The elemental composition of Shilajit was conducted using three advanced analytical techniques (LIBS, ICP, and EDX). For the comparative studies, the two Shilajit kinds mostly sold globally produced in India and Pakistan were collected. Our main focus is to highlight nutritional eminence and contamination of heavy metals to hinge on Shilajit therapeutic potential. In this work, laser-induced breakdown spectroscopy (LIBS) was applied for qualitative and quantitative analysis of the Shilajit. Our LIBS analysis revealed that Shilajit samples composed of several elements like Ca, S, K, Mg, Al, Na, Sr, Fe, P, Si, Mn, Ba, Zn, Ni, B, Cr, Co, Pb, Cu, As, Hg, Se, and Ti. Indian and Pakistani Shilajits were highly enriched with Ca, S, and K nutrients and contained Al, Sr, Mn, Ba, Zn, Ni, B, Cr, Pb, As, and Hg toxins in amounts that exceeded the standard permissible limit. Even though the content of most elements was comparable among both Shilajits, nutrients, and toxins, in general, were accentuated more in Indian Shilajit with the sole detection of Hg and Ti. The elemental quantification was done using self-developed calibration-free laser-induced breakdown spectroscopy (CF-LIBS) method, and LIBS results are in well agreement with the concentrations determined by standard ICP-OES/MS method. To verify our results by LIBS and ICP-OES/MS techniques, EDX spectroscopy was also conducted which confirmed the presence above mentioned elements. This work is highly significant for creating awareness among people suffering due to overdose of this product and save many human lives.

Uranium corrosion characterization by handheld laser-induced breakdown spectroscopy

A commercial-off-the-shelf handheld laser-induced breakdown spectroscopy system was modified, calibrated and tested for discrimination between uranium oxide and uranium hydride when assessing uranium corrosion products. Operating parameters, system modifications, and onboard data analysis were developed to accomplish the analytical task. This work represents the first laser-induced breakdown spectroscopy analysis of bulk uranium hydride, a pyrophoric material, within an inert glovebox. Finally, the work shown here illustrates a rapid identification technique for uranium corrosion types from pure UO2 or U3O8 to pure UH3.

Trace-element imaging at macroscopic scale in a Belgian sphalerite-galena ore using Laser-Induced Breakdown Spectroscopy (LIBS)

Laser-Induced Breakdown Spectroscopy (LIBS) is a fast in-situ analytical technique based on spectroscopic analysis of atomic emission in laser-induced plasmas. Geochemical mapping at macroscopic scale using LIBS was applied to a decimetric Zn-Pb ore sample from east Belgium, which consists of alternating sphalerite and galena bands. A range of elements was detected with no or minimal spectral correction, including elements of interest for beneficiation such as Ge, Ag and Ga (although the detection of gallium could not be confirmed), and remediation, especially As and Tl. The comparison between LIBS and Energy Dispersive Spectroscopy (EDS) analyses showed that LIBS intensities reliably relate to elemental concentration although differences in spot size and detection limits exist between both techniques. The elemental images of minor and trace elements (Fe, Cu, Ag, Cd, Sb, As, Tl, Ge, Ni and Ba) obtained with LIBS revealed with great detail the compositional heterogeneity of the ore, including growth zones that were not visible on the specimen. In addition, each mineral generation has a distinct trace-element composition, reflecting a geochemical sequence whose potential metallogenic significance at the district scale should be addressed in further work. Although qualitative and preliminary, the obtained LIBS dataset already produced a wealth of information that allowed to initiate discussion on some genetical and crystallochemical aspects. Above all, LIBS appears as a powerful tool for screening geochemically large samples for the selection of zones of particular interest for further analysis.

From machine learning to transfer learning in laser-induced breakdown spectroscopy analysis of rocks for Mars exploration

With the ChemCam instrument, laser-induced breakdown spectroscopy (LIBS) has successively contributed to Mars exploration by determining the elemental compositions of soils, crusts, and rocks. The American Perseverance rover and the Chinese Zhurong rover respectively landed on Mars on February 18 and May 15, 2021, further increase the number of LIBS instruments on Mars. Such an unprecedented situation requires a reinforced research effort on the methods of LIBS spectral data analysis. Although the matrix effects correspond to a general issue in LIBS, they become accentuated in the case of rock analysis for Mars exploration, because of the large variation of rock compositions leading to the chemical matrix effect, and the difference in surface physical properties between laboratory standards (in pressed powder pellet, glass or ceramic) used to establish calibration models and natural rocks encountered on Mars, leading to the physical matrix effect. The chemical matrix effect has been tackled in the ChemCam project with large sets of laboratory standards offering a good representation of various compositions of Mars rocks. The present work more specifically deals with the physical matrix effect which is still lacking a satisfactory solution. The approach consists in introducing transfer learning in LIBS data treatment. For the specific application of total alkali-silica (TAS) classification of rocks (either with a polished surface or in the raw state), the results show a significant improvement in the ability to predict of pellet-based models when trained together with suitable information from rocks in a procedure of transfer learning. The correct TAS classification rate increases from 25% for polished rocks and 33.3% for raw rocks with a machine learning model, to 83.3% with a transfer learning model for both types of rock samples.

X-ray Fluorescence and Laser-Induced Breakdown Spectroscopy Analysis of Li-Rich Minerals in Veins from Argemela Tin Mine, Central Portugal

In this work, X-ray fluorescence (XRF) and Laser-induced breakdown spectroscopy (LIBS) analyses were applied to samples of quartz, montebrasite, and turquoise hydrothermal veins in the Argemela Tin Mine (Central Portugal). Montebrasite (LiAl(PO4)(OH,F)) is potentially the main ore mineral; with its alteration, lithium (Li) can disseminate into other minerals. A hand sample was cut and analyzed by XRF and LIBS for several elements of interest including Cu, P, Al, Si, and Li. Although XRF cannot measure Li, results from its analysis are effective for distinguishing turquoise from montebrasite. LIBS analysis complemented this study, making it possible to conclude that turquoise does not contain any significant Li in its structure. The difference in spot size between the techniques (5 mm vs. 300 µm for XRF and LIBS, respectively) resulted in a poorer performance by XRF in accurately identifying mixed minerals. A thin section was petrographically characterized and mapped using LIBS. The mapping results demonstrate the possibility of the successful identification of minerals and their alterations on a thin section. The results of XRF analysis and LIBS mapping in petrographic sections demonstrate the efficacy of these methods as tools for element and mineral identification, which can be important in exploration and mining phases, complementing more traditional techniques.

Classification of coal deposited epoxy micro-nanocomposites by adopting machine learning techniques to LIBS analysis

Epoxy micro-nanocomposite specimens incorporated with 66 wt% of silica micro fillers and 0.7 wt% of ion trapping particles as nano fillers, are coated with four different variants of coal. The conductivity of the coal deposited samples is observed to be in direct correlation with the percentage carbon content present in the coal samples. The epoxy micro-nanocomposite specimens coated with different variants of coals were successfully classified by using Laser induced breakdown spectroscopy (LIBS) assisted by various machine learning techniques. It is noticed that the classification through Logistic regression method (LRM) has reflected a higher training as well as testing accuracy of 100% and 98%, respectively when compared to other machine learning methods.

LIBS Monitoring and Analysis of Laser-Based Layered Controlled Paint Removal from Aircraft Skin

Reliability and controllability of selective removal of multiple paint layers from the surface of aircraft skin depend on effective online monitoring technology. An analysis was performed on the multi-pulse laser-induced breakdown spectroscopy (LIBS) on the surface of the aluminum alloy substrate, primer, and topcoat. Based on that, an exploration was conducted on the changes of the characteristic peaks corresponding to the characteristic elements that are contained in the topcoat, primer, and substrate with different layers of a laser action, in combination with analysis of microscopic morphology, composition, and depth of laser multi-pulse pits. The results show that the appearance and increase of the characteristic peak intensity of the Ca I at the wavelength of 422.7 nm can be regarded as the basis for the complete removal of the topcoat; the decrease or disappearance of the characteristic peak intensity can be regarded as the basis for the complete removal of the primer. Al I spectrum at the wavelength of 394.5 nm and 396.2 nm can be adopted to characterize the degree of damage to the aluminum alloy substrate. The feasibility and accuracy of the LIBS technology for the laser selective paint removal process and effect monitoring of aircraft skin were verified. Demonstrating that under the premise of not damaging the substrate, laser-based layered controlled paint removal (LLCPR) from aircraft skin can be achieved by monitoring the spectrum and composition change law of specified wavelength position corresponding tothe characteristic elements that are contained in the specific paint layer.

Identification of meat species in processed meat products by using protein based laser induced breakdown spectroscopy assay

The detection of meat fraud and mislabeling in processed meat products is a raising concern for consumers. The aim of this study was to develop and demonstrate the potential of protein-based laser induced breakdown spectroscopy (LIBS) method to be used for the identification of beef, chicken, and pork in fermented sausage and salami products. In this respect, bulk protein and protein fractions rich in sarcoplasmic and myofibrillar protein of sausage and salami products were obtained and subjected to LIBS analysis. LIBS spectrum was evaluated with chemometric methods to classify meat species and determine adulteration ratio by using principal component analysis and partial least square analysis, respectively. Limit of detection values for chicken and pork adulteration in beef sausage were found as 3.68 and 3.83% for myofibrillar fraction, while those values in beef salami were found as 3.80 and 3.47% for sarcoplasmic fraction, respectively.

Exploring an Application of Principal Component Analysis to Laser-Induced Breakdown Spectroscopy of Stainless-Steel Standard Samples as a Research Project

Laser-induced breakdown spectroscopy (LIBS) and principal component analysis (PCA) are frequently used for analytical purposes in research and industry, but they seldom are part of the chemistry curriculum or laboratory exercises. This case study paper describes the combined application of LIBS and PCA during a research internship for an undergraduate student. The instructional method applied was based on a one-on-one mentorship, in which case the learner was engaged in a research work. The learning activities included theoretical introductions to the LIBS and PCA methods, numerical simulation, experiments, and data analysis. The study covered three main topics: analysis of LIBS spectra, application of PCA for clustering, and use of PCA for experimental design. The realization of the study was instructive for all parties involved: from the mentorship point of view, it is concluded that the topics can be covered during an internship or developed into a one semester long research-based module of a chemistry program or a final year project. The student, on the other hand, developed profound technical skills in performing experiments and using PCA software for data analysis.

The Planetary Terrestrial Analogues Library (PTAL) – An exclusive lithological selection of possible martian earth analogues

The Planetary Terrestrial Analogues Library (PTAL) is a dedicated lithological collection that currently consists of 102 terrestrial rock samples selected to be possible Mars analogues. The ultimate goal is improving future remote mineralogical and petrological analysis on Mars and other planetary bodies based on selected analysis such as Near- Infrared Reflectance Spectroscopy (NIR), Raman spectroscopy, Laser Induced Breakdown Spectroscopy (LIBS) and X-ray diffraction (XRD).Most international standards applied in the remote martian mineralogical and petrological analysis have so far been based on single, pure mineral analysis, with minimal interferences from other naturally occurring minerals. Here we present detailed lithological sample evaluations based on field appearance along with optical and XRD analysis of key terrestrial rock types. The detailed mineralogical and petrological descriptions give good basis for more complete lithological understanding. In combination with NIR, LIBS and Raman analysis of the very same samples PTAL aims at improving mineralogical and petrographical information from future rovers on Mars e.g. NASA's Mars2020-Perseverance and ESA and Roscosmos's ExoMars - Rosalind Franklin.The PTAL sample collection covers exclusively collected volcanic, magmatic and various sedimentary rocks and regoliths from well-known locations all over the world. These samples have a general composition comparable to what is currently known from Mars. The strength of this sample collection is its origin as common whole rock samples, in which minerals occur in their natural settings. It thereby allows studying possible detection interferences and a comparison of the sensitivity of the different techniques. The collection, in addition, forms the base for various alteration studies to better understand and explain alteration and weathering conditions on Mars.The complete results and sample preparations will be available to all scientists interested.

Identification of 20 polymer types by means of laser-induced breakdown spectroscopy (LIBS) and chemometrics

Over the past few years, laser-induced breakdown spectroscopy (LIBS) has earned a lot of attention in the field of online polymer identification. Unlike the well-established near-infrared spectroscopy (NIR), LIBS analysis is not limited by the sample thickness or color and therefore seems to be a promising candidate for this task. Nevertheless, the similar elemental composition of most polymers results in high similarity of their LIBS spectra, which makes their discrimination challenging. To address this problem, we developed a novel chemometric strategy based on a systematic optimization of two factors influencing the discrimination ability: the set of experimental conditions (laser energy, gate delay, and atmosphere) employed for the LIBS analysis and the set of spectral variables used as a basis for the polymer discrimination. In the process, a novel concept of spectral descriptors was used to extract chemically relevant information from the polymer spectra, cluster purity based on the k-nearest neighbors (k-NN) was established as a suitable tool for monitoring the extent of cluster overlaps and an in-house designed random forest (RDF) experiment combined with a cluster purity–governed forward selection algorithm was employed to identify spectral variables with the greatest relevance for polymer identification. Using this approach, it was possible to discriminate among 20 virgin polymer types, which is the highest number reported in the literature so far. Additionally, using the optimized experimental conditions and data evaluation, robust discrimination performance could be achieved even with polymer samples containing carbon black or other common additives, which hints at an applicability of the developed approach to real-life samples.Graphical abstract

The effect of ablation angle on intensity of laser-induced breakdown spectroscopy under vacuum

The in situ diagnostic of the composition and content of the first wall materials in tokamak devices is an important research interest of the plasma-wall interaction. Laser-induced breakdown spectroscopy (LIBS) has become an attractive tool for in situ diagnostic of the first wall materials. It has the ability to analyze the composition of the first wall remotely and on-line without sample manipulation or pretreatment. In tokamak, using the LIBS method in a fixed window to diagnose wall materials in different positions will inevitably affect the LIBS measurement signal due to different laser ablation and light collection angles. In this paper, we got the determination of the relationship between the intensity of the tungsten spectral line and laser energy in the laboratory as a prerequisite. And the effects of different ablation angles on the temporal evolution of the spectrum of the laser ablated tungsten material were investigated in detail. This provides a reference for in situ LIBS analysis.

Rapid Analysis of Chemical Composition and Physical Properties of Gemstones Using LIBS and Chemometric Technique

Laser-induced breakdown spectroscopy (LIBS), accompanied by chemometric data analysis, is used to identify and classify gemstones of various hardness. The study involves several gemstones: amethyst, aquamarine beryl, bloodstone citrine, diopside, and enstatite. Their hardness is determined through a correlation utilizing the spectral intensity ratio of the ionic to atomic spectral lines of an identified element in the LIB spectrum. The result of the relative hardness obtained from the LIBS analysis is in good agreement with the hardness measured from Mohs’s scale of hardness, a popular qualitative method to determine hardness. In this work, a linear relationship has been established between the Mohs’s hardness and the plasma excitation temperature. Thus, the hardness of the gemstones can be determined with the help of plasma excitation temperature. Moreover, the analysis of trace elements in LIB spectral data reveals that a particular element is responsible for the colors of gemstones. Therefore, the relative concentration of constituents is calculated for all gemstones and compared. Principal component analysis (PCA) is successfully applied to all gemstone spectra for rapid classification and discrimination based on their variable elemental concentrations and respective hardness.