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This study was dedicated to developing analytical methods for determining macronutrients (Ca, K, and Mg) in soy leaf samples with and without petioles. The study's primary purpose was to present Laser-induced breakdown spectroscopy (LIBS) as a viable alternative for directly analyzing leaf samples using chemometric tools to interpret the data obtained. The instrumental condition chosen for LIBS was 70 mJ of laser pulse energy, 1.0 µs of delay time, and 100 µm of spot size, which was applied to 896 samples: 305 of soy without petioles and 591 of soy with petioles. The reference values of the analytes for the proposition of calibration models were obtained using inductively coupled plasma optical emission spectroscopy (ICP-OES) technique. Twelve normalization modes and two calibration strategies were tested to minimize signal variations and sample matrix microheterogeneity. The following were studied: multivariate calibration using partial least squares and univariate calibration using the area and height of several selected emission lines. The notable normalization mode for most models was the Euclidean norm. No analyte showed promising results for univariate calibrations. Micronutrients, P and S, were also tested, and no multivariate models presented satisfactory results. The models obtained for Ca, K, and Mg showed good results. The standard error of calibration ranged from 2.3 g/kg for Ca in soy leaves without petioles with two latent variables to 5.0 g/kg for K in soy leaves with petioles with two latent variables.

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The contamination of aquatic environments with heavy metals is an important issue, and in turn, it is crucial to study remediation techniques that can be applied in situ. In this work, the use of a containment system with macrophytes Limnobium laevigatum is explored in the laboratory to evaluate the remotion of Cr in contaminated sediments. The roots of the plants were placed in contact with the bottom sediment through a containment system. The concentration of Cr in macrophyte and sediment samples exposed to different exposure times (1, 4 and 7 days) was determined by laser-induced breakdown spectroscopy technique. The initial concentration of Cr in the sediment was 112 ± 5 mg/kg and decreased by 65% to the control (p < 0.05) after 24 h of exposure. The removal continued throughout the study time until reaching values of 23 ± 1 mg/kg. In macrophytes, the Cr concentration increased from 20 ± 5 mg/kg to 2066 ± 216 mg/kg after seven days of exposure. The correlation coefficient between Cr concentrations in both matrices was -0.96. Finally, the bioaccumulation factor of Cr in L. laevigatum was 95.22 ± 8.51. Therefore, the system studied could be a potential tool to remedy the bottom sediments of streams and lakes contaminated with heavy metals in situ.

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This paper describes the effects of laser pulse rate and solution flow rate on the determination of lithium at high pressure for water and 2.5% sodium chloride solutions using laser-induced breakdown spectroscopy (LIBS). Preliminary studies were performed with 0-40 mg L-1 Li solutions, at ambient pressure and at 210 bar, and in static and flowing (6 mL · min-1) regimes, for a combination of four different measurement conditions. The sensitivity of calibration curves depended on the pressure and the flow rate, as well as the laser pulse rate. The sensitivity of the calibration curve increased about 10% and 18% when the pressure was changed from 1 to 210 bar for static and flowing conditions, respectively. However, an effect of flow rate at high pressure for both 2 and 10 Hz laser pulse rates was observed. At ambient pressure, the effect of flow rate was negligible, as the sensitivity of the calibration curve decreased around 2%, while at high pressure the sensitivity increased around 4% when measurements were performed in a flow regime. Therefore, it seems there is a synergistic effect between pressure and flow rate, as the sensitivity increases significantly when both changes are considered. When the pulse rate is changed from 2 to 10 Hz, the sensitivity increases 26-31%, depending on the pressure and flow conditions. For lithium detection limit studies, performed with a laser pulse energy of 2.5 mJ, repetition rate of 10 Hz, gate delay of 500 ns, gate width of 1000 ns, and 1000 accumulations, a value around 40 µg L-1 was achieved for Li solutions in pure water for all four measurement conditions, while a detection limit of about 92 µg L-1 was determined for Li in 2.5% sodium chloride solutions, when high pressure and flowing conditions were employed. The results obtained in the present work demonstrate that LIBS is a powerful tool for the determination of Li in deep ocean conditions such as those found around hydrothermal vent systems.

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The correct recognition of sweet orange (Citrus sinensis L. Osbeck) variety accessions at the nursery stage of growth is a challenge for the productive sector as they do not show any difference in phenotype traits. Furthermore, there is no DNA marker able to distinguish orange accessions within a variety due to their narrow genetic trace. As different combinations of canopy and rootstock affect the uptake of elements from soil, each accession features a typical elemental concentration in the leaves. Thus, the main aim of this work was to analyze two sets of ten different accessions of very close genetic characters of three varieties of fresh citrus leaves at the nursery stage of growth by measuring the differences in elemental concentration by laser-induced breakdown spectroscopy (LIBS). The accessions were discriminated by both principal component analysis (PCA) and a classifier based on the combination of classification via regression (CVR) and partial least square regression (PLSR) models, which used the elemental concentrations measured by LIBS as input data. A correct classification of 95.1% and 80.96% was achieved, respectively, for set 1 and set 2. These results showed that LIBS is a valuable technique to discriminate among citrus accessions, which can be applied in the productive sector as an excellent cost-benefit tool in citrus breeding programs.

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The branching ratio method is usually used to evaluate the optical thinness conditions in laser-generated plasmas, which are important for the application of analytical methods such calibration free laser induced breakdown spectroscopy (CF-LIBS). In this communication, we warn on the possibility that in some circumstances, the branching-ratio method might give results close to the one characterizing optically thin plasma conditions, even in the presence of a substantial self-absorption for the transitions considered.

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Pottery sherds from Teotihuacan, Mexico, belonging to the Formative and Classic periods (150 BCE-700 CE) were investigated using laser-induced breakdown spectroscopy (LIBS) and inductively coupled plasma optical emission spectrometry (ICP-OES). LIBS results show that most of the investigated samples have primarily the same elemental composition. Nevertheless, there are also a few sherds that could be associated to foreign ceramic groups with characteristic concentrations of Na, K, Ca, Mn, Rb, and Sr. The relative elemental composition of red pigments applied on ceramic bodies was also analyzed through a LIBS depth profiling. Diverse hematite-based pigments were distinguished according to the detected iron content. Hematite was also combined with red soils with a high relative content of Mn, Sr, Ba, or Ti. The ICP-OES analysis of ceramic pastes is consistent with the emission intensities obtained using LIBS. Principal component analysis indicates that all samples identified as locals belong to a single chemical group. Moreover, locally made ceramics and the analyzed clays from the nearby area have the same elemental composition, which appears clearly differentiated from imported samples.

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In this study, hybrid poly(dimethylsiloxane)-derived hydroxyurethanes films (PDMSUr-PWA) containing phosphotungstic acid (H3PW12O40/PWA) were characterized using field emission gun scanning electron microscopy (FEG-SEM), in attenuated total reflectance Fourier transform mid-infrared mode (ATR FT-MIR), and analyzed using synchrotron radiation micro-X-ray fluorescence (SR-µXRF), synchrotron radiation grazing incidence X-ray fluorescence (SR-GIXRF), laser-induced breakdown spectroscopy (LIBS), and instrumental neutron activation analysis (NAA) in order to correlate the distribution patterns of tungsten and properties of PDMSUr-PWA films. PDMS constitute elastomers with good mechanical, thermal, and chemical (hydrophobicity/non-hygroscopy) resistance. Currently, products based on urethanes (e.g., polyurethanes) are widely used in many applications as plastics, fiber-reinforced polymers, high-performance adhesives, corrosion-resistant coatings, photochromic films, among others. The possibility to combine inorganic and organic components can produce a hybrid material with unique properties. PWA has an important role as agent against the corrosion of steel surfaces in different media, besides exhibiting amazing catalytic and photochromic properties in these films. PWA kept its structure inside of these hybrid films through interactions between the organic matrix of PDMSUr and silanol from the inorganic part (organically modified silica), as was shown using ATR FT-MIR spectra. The FEG-SEM/SR-µXRF/wide-angle X-ray scattering (WAXS)/X-ray diffraction (XRD)/energy dispersive X-ray results proved the presence of PWA in the composition of domains of PDMSUr-PWA films. At PWA concentrations higher than 50 wt%/wt, tungsten segregation across the thickness is predominant, while that at PWA concentrations lower than 35 wt%/wt, tungsten segregation at surface is predominant. Inhomogeneities in the tungsten distribution patterns (at micrometric and millimetric level) may play an important role in the mechanical properties of these films (elastic modulus and hardness).

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A laser-induced breakdown spectroscopy (LIBS) technique was used to evaluate the filler content in particulate epoxy-copper composites. A potential application for a direct and fast measurement of the filler in composites through the LIBS results is suggested using calibrated samples. The methodology used in this work makes possible the incorporation of LIBS as a quantitative technique for the study of particle metal-filled epoxy composites, providing a method to obtain a direct estimation of the filler volume fraction.

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In this work, we suggest a methodology to determine the impact parameter for neutral dysprosium emission lines from the characterization of the plasma generated by laser ablation in a sealed chamber filled with argon. The procedure is a combination of known consistent spectroscopic methods for plasma temperature determination, electron density, and species concentration. With an electron density of 3.1 × 1018 cm-3 and temperature close to 104 K, we estimated the impact electron parameter for nine spectral lines of the neutral dysprosium atom. The gaps in the impact parameter data in the literature, mainly for heavy elements, stress the importance of the proposed method.

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The tanning industry is one of the largest environmental polluters due to high generation waste in all production processes, but the tanning is particularly worrisome due to the use of significant amounts of chromium. Cr is an element potentially toxic to both health and the environment, depending on the concentration and the oxidation state. Cr(VI) can come in contact with human skin when using leather goods, which can cause allergies and dermatitis, besides being carcinogenic. Considering that approximately 90% of the world production of leather is performed with Cr salts, the determination of this element in leather is necessary to avoid exposure to the risks that the element can provide. The main goal of this study was the development of an alternative analytical method for the determination of Cr in leathers (ovine and bovine leather tanned with Cr and vegetable tannin) using wavelength dispersive X-ray fluorescence (WDXRF) for direct solid analysis. Besides performing analysis of the chemical composition and determination of Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Ni, Pb, Sb, Sr, Ti, and Zn in leather by inductively coupled plasma optical emission spectrometry (ICP OES). Principal component analysis (PCA) was also used in the evaluation of the WDXRF and ICP OES data sets. WDXRF calibration models for Cr presented satisfactory figures of merit and the analysis of the leathers revealed an alarming concentration of total Cr in the samples reaching 21,353 mg kg-1.

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Solder masks are essential materials used in the manufacture of printed circuit boards (PCB). This material protects PCBs against several types of damage and performance failure. In this study, the capabilities of laser-induced breakdown spectroscopy (LIBS) were investigated for the direct analysis of solder masks typically commercialized for homemade PCB production, and inductively coupled plasma-optical emission spectrometry (ICP-OES) was used to obtain a chemical profile for the target analytes Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Sb, Sn, and Zn. Inductively coupled plasma-mass spectrometry (ICP-MS) was also employed for the determination of potentially toxic elements, such as As, Cd, Cr, Pb, and Hg. In addition to the qualitative information that may be useful for obtaining the spectral profile related to the raw materials present in solder masks formulations, LIBS was also applied for major elements (Al, Ba, Cu, Fe, Mg, and Zn) determination, but due to the low sensitivity, the obtained results were only semi-quantitative for Ba. Regarding Cd, Cr, Hg, and Pb, the samples analyzed were following the restriction of hazardous substances (RoHS) directive of the European Union.

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Synthetic leather samples from Brazil and Paraguay were evaluated in this study using three spectroscopy techniques: inductively coupled plasma optical emission spectrometry (ICP-OES), laser-induced breakdown spectroscopy (LIBS), and wavelength dispersive X-ray fluorescence (WDXRF). The obtained information from each technique was separately inspected with principal component analysis (PCA). The concentrations of the elements determined in the synthetic leathers using ICP-OES decreased in the following order: Ca > Cr > Mg > Ba > Pb > Al > Fe > Zn > Sb > Ni with a concentration range below the limit of quantification (

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Due to the continual increase in waste generated from electronic devices, the management of plastics, which represents between 10 and 30% by weight of waste electrical and electronic equipment (WEEE or e-waste), becomes indispensable in terms of environmental and economic impacts. Considering the importance of acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), and their blends in the electronics and other industries, this study presents a new application of laser-induced breakdown spectroscopy (LIBS) for the fast and direct determination of PC and ABS concentrations in blends of these plastics obtained from samples of e-waste. From the LIBS spectra acquired for the PC/ABS blend, multivariate calibration models were built using partial least squares (PLS) regression. In general, it was possible to infer that the relative errors between the theoretical or reference and predicted values for the spiked samples were lower than 10%.

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This work proposes a method to perform elemental identification on plasmas produced using the laser-induced breakdown spectroscopy (LIBS) technique. The method is based on the preservation of the relative relevance of the spectral line emission intensities, which is lost during the parametric correlation procedure, by the introduction of a similitude coefficient called wavelength similarity coefficient. Furthermore, it was shown that for identification purposes, a simplified plasma model is sufficient to predict adequately the relative emission intensities in LIBS plasmas. As a result, it is possible to automatically identify the species with high emission signals, while trace detection is also possible by relaxing search conditions, although manual refinement is still required.

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Huanglongbing (HLB) is the most recent and destructive bacterial disease of citrus and has no cure yet. A promising alternative to conventional methods is to use laser-induced breakdown spectroscopy (LIBS), a multi-elemental analytical technique, to identify the nutritional changes provoked by the disease to the citrus leaves and associate the mineral composition profile with its health status. The leaves were collected from adult citrus trees and identified by visual inspection as healthy, HLB-symptomatic, and HLB-asymptomatic. Laser-induced breakdown spectroscopy measurements were done in fresh leaves without sample preparation. Nutritional variations were evaluated using statistical tools, such as Student's t-test and analysis of variance applied to LIBS spectra, and the largest were found for Ca, Mg, and K. Considering the nutritional profile changes, a classifier induced by classification via regression combined with partial least squares regression was built resulting in an accuracy of 73% for distinguishing the three categories of leaves.

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This work presents a new method for forward variable selection and calibration and its evaluation for manganese determination in steel by laser-induced breakdown spectroscopy (LIBS). A compact and low-cost LIBS instrument was used, based on a microchip laser and a grating mini-spectrometer containing a non-intensified, non-gated, and non-cooled linear sensor array. Sixty steel samples were analyzed, with known manganese concentrations from 0.106 to 1.696 wt%. The spectra (1757 variables between 200 and 850 nm) were acquired under the continuous application of laser pulses at 100 Hz and using 80, 400, and 1000 ms integration times. The new method generated a mathematic combination of the selected variables and the results were calibrated against the manganese content by linear or quadratic regression. The best results were obtained using the spectra from all integration times together, with 31 selected variables and root mean square errors of cross-validation and prediction of 0.015 and 0.033, respectively. Compared to Jack-knife partial least squares regression, the new method presented lower prediction errors and numbers of selected variables, with the advantages of no data pretreatment and a simpler mathematic calculation. Graphical abstract New method for forward variable selection and calibration applied to manganese determination in steel by laser induced breakdown spectroscopy.

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This study describes the application of laser-induced breakdown spectroscopy (LIBS) for the direct determination of Ca, K and Mg in powdered milk and solid dietary supplements. The following two calibration strategies were applied: (i) use of the samples to calculate calibration models (milk) and (ii) use of sample mixtures (supplements) to obtain a calibration curve. In both cases, reference values obtained from inductively coupled plasma optical emission spectroscopy (ICP OES) after acid digestion were used. The emission line selection from LIBS spectra was accomplished by analysing the regression coefficients of partial least squares (PLS) regression models, and wavelengths of 534.947, 766.490 and 285.213nm were chosen for Ca, K and Mg, respectively. In the case of the determination of Ca in supplements, it was necessary to perform a dilution (10-fold) of the standards and samples to minimize matrix interference. The average accuracy for powdered milk ranged from 60% to 168% for Ca, 77% to 152% for K and 76% to 131% for Mg. In the case of dietary supplements, standard error of prediction (SEP) varied from 295 (Mg) to 3782mgkg-1 (Ca). The proposed method presented an analytical frequency of around 60 samples per hour and the step of sample manipulation was drastically reduced, with no generation of toxic chemical residues.

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A simple device based on two commercial laser pointers is described to assist in the analysis of samples that present uneven surfaces and/or irregular shapes using laser-induced breakdown spectroscopy (LIBS). The device allows for easy positioning of the sample surface at a reproducible distance from the focusing lens that conveys the laser pulse to generate the micro-plasma in a LIBS system, with reproducibility better than ±0.2 mm. In this way, fluctuations in the fluence (J cm-2) are minimized and the LIBS analytical signals can be obtained with a better precision even when samples with irregular surfaces are probed.

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In this work the diffusion of mercury and other elements from amalgam tooth restorations through the surrounding dental tissue (dentin) was evaluated using femtosecond laser-induced breakdown spectroscopy (fs-LIBS). To achieve this, seven deciduous and eight permanent extracted human molar teeth with occlusal amalgam restorations were half-sectioned and analyzed using pulses from a femtosecond laser. The measurements were performed from the amalgam restoration along the amalgam/dentin interface to the apical direction. It was possible to observe the presence of metallic elements (silver, mercury, copper and tin) emission lines, as well as dental constituent ones, providing fingerprints of each material and comparable data for checking the consistence of the results. It was also shown that the elements penetration depth values in each tooth are usually similar and consistent, for both deciduous and permanent teeth, indicating that all the metals diffuse into the dentin by the same mechanism. We propose that this diffusion mechanism is mainly through liquid dragging inside the dentin tubules. The mercury diffused further in permanent teeth than in deciduous teeth, probably due to the longer diffusion times due to the age of the restorations. It was possible to conclude that the proposed femtosecond-LIBS system can detect the presence of metals in the dental tissue, among the tooth constituent elements, and map the distribution of endogenous and exogenous chemical elements, with a spatial resolution that can be brought under 100 µm.

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Contaminants (Cd, Cr, and Pb) as well as minor (B, Cu, Mn, Na, and Zn) and major (Ca and Mg) elements were directly determined in solid fertilizer samples using laser-induced breakdown spectroscopy (LIBS). Factorial designs were used to define the most appropriate LIBS parameters and pellet pressure on solid fertilizers. Emission lines for all of the analytes were collected and employed 12 signal normalization modes. The best results were obtained using a laser energy of 75 mJ, a spot size of 50 µm, a pressure of 10 t/in., and a delay of 2.0 µs. Good correlation was obtained between the calibration model's prediction using the proposed LIBS method and the reference values obtained with ICP-OES. The limits of detection (LOD) for the proposed method varied from 2 mg/kg (for Cd) to 1% (for Zn).