Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

{"title":"Double Pulse laser-induced breakdown spectroscopy (DP-LIBS): A Comprehensive technique Review","authors":"Muhammad Rizwan ,&nbsp;Muhammad Sher Afgan ,&nbsp;Seher Saleem ,&nbsp;Kaikai Kou ,&nbsp;Zongyu Hou ,&nbsp;Zhe Wang","doi":"10.1016/j.sab.2025.107168","DOIUrl":"10.1016/j.sab.2025.107168","url":null,"abstract":"<div><div>Double pulse-laser induced breakdown spectroscopy (DP-LIBS) is one of the most widely adopted variants of laser-induced breakdown spectroscopy for rapid elemental analysis. DP-LIBS is an effective way of improving the emission line intensities and increasing the analytical capabilities of conventional LIBS. We comprehensively overviewed different aspects of DP-LIBS from fundaments to applications. The key mechanisms of pre-ablation, reheating, and interpulse delay have been discussed. Different geometrical configurations for the two pulses including collinear, cross-beam, orthogonal pre-ablation, and orthogonal reheating are outlined. The pulse durations of the ablating laser have a huge impact on the ablation process, thus, the effects of the temporal settings of the laser pulse duration are explained. This includes ns-ns, fs-fs, fs-ns, and long short DP-LIBS. The impacts of double-pulse LIBS on the ablation process and analytical outcomes such as signal intensity, repeatability, ablation rate, crater and plasma size, and plasma parameters are encapsulated. Finally, several DP-LIBS applications from metal and alloy analysis and explosive detection to industrial analysis have been stipulated. DP-LIBS approach results in a notable enhancement in the emission intensity; however, repeatability is a key parameter to consider for meaningful applications. Among different temporal configurations, long-short DP-LIBS provides relatively smoother and greater interaction of the laser beam with the plasma plume and sample, hence giving a more temporally efficient energy delivery to the plasma and sample making it more suitable for intensity enhancement and signal improvement among other variants.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107168"},"PeriodicalIF":3.2,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimization of denoising approaches in the context of ultra-fast LIBS imaging","authors":"Ruggero Guerrini ,&nbsp;Cesar Alvarez-Llamas ,&nbsp;Lucie Sancey ,&nbsp;Vincent Motto-Ros ,&nbsp;Ludovic Duponchel","doi":"10.1016/j.sab.2025.107167","DOIUrl":"10.1016/j.sab.2025.107167","url":null,"abstract":"<div><div>Laser-Induced Breakdown Spectroscopy (LIBS) has emerged as a powerful analytical tool capable of providing multi-elemental information from a single laser pulse with minimal sample preparation. This technique generates a laser-induced, transient plasma on the sample surface, whose spectral emission is analyzed to determine its elemental composition. μLIBS-Imaging, a variant offering spatially resolved elemental analysis, holds promise for applications in diverse fields such as industry, geology, forensics, and biomedicine. Our drive to go ever faster and analyze increasingly larger areas of interest in samples now compels us to use kHz lasers for this elemental imaging. Despite its potential, implementing such lasers in μLIBS-imaging would face diverse challenges mainly related to weak plasma emission and signal-to-noise ratio (SNR) degradation, particularly when applied to delicate biological samples. This paper investigates methods to enhance SNR in fast μLIBS imaging, particularly for biomedical applications. We focus on denoising techniques suitable for high-frequency laser applications, comparing methods like Savitzky-Golay smoothing, Fast Fourier Transform, wavelet-based filtering, Whittaker Filtering, and Principal Component Analysis (PCA). Our strategy optimizes denoising parameters for specific elemental emission peaks, enhancing SNR for individual elements of interest. The results demonstrate significant improvements in data quality, paving the way for more accurate and efficient elemental imaging in complex biomedical specimens.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107167"},"PeriodicalIF":3.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Outside Front Cover - Journal name, Cover image, Volume issue details, ISSN, Cover Date, Elsevier Logo and Society Logo if required","authors":"","doi":"10.1016/S0584-8547(25)00045-X","DOIUrl":"10.1016/S0584-8547(25)00045-X","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107160"},"PeriodicalIF":3.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monte Carlo simulations of energy dispersive X-ray fluorescence (EDXRF) of liquid and metallic samples: A comparison and experimental validation of MCNP and XRMC codes","authors":"P. Zambianchi ,&nbsp;M. Antoniassi ,&nbsp;F.L. Melquiades ,&nbsp;J.K. Zambianchi","doi":"10.1016/j.sab.2025.107157","DOIUrl":"10.1016/j.sab.2025.107157","url":null,"abstract":"<div><div>The present study compares numerical simulations carried out by two Monte Carlo codes, the Monte Carlo N-Particle (MCNP) and the XRMC, of Energy Dispersive X-ray fluorescence (EDXRF) excited in liquid and metallic samples. The results are validated by measurements with a laboratory-made equipment, consisting of a mini X-ray tube (Moxtek, Inc., 4 W, Ag target) and a Si PIN detector model X123 (Amptek, Inc.), configured in the usual 45°/45° geometry. The liquid sample was a multielementar stock solution from High Purity Standards containing traces of the transition metals Cu, Fe, Mn, and Zn. For the solid samples, two metallic plates of standard reference materials were used, namely, a) a rectangular plate (6.9 mm × 43.4 mm, 1.5 mm thick) made of high purity copper; and b) a steel alloy plate (Duplex 2205 CRM) containing Si, Cr, Mn, Fe, Ni, Cu and Mo in its composition. The quantitative analysis of the relative peak intensities between the simulations and experiment reveals a difference of 0.4 % to 12.3 %, depending on the elemental characteristic line and sample composition. The results show an overall very good agreement between the simulations of the MCNP and XRMC codes with the experimental spectra, making them suitable for typical EDXRF applications involving metallic samples and multielement aqueous solutions.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107157"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"General regularities in the behavior of the rare gas spectra in alternating electric fields","authors":"E.V. Koryukina","doi":"10.1016/j.sab.2025.107155","DOIUrl":"10.1016/j.sab.2025.107155","url":null,"abstract":"<div><div>The behavior of the atomic emission spectra in alternating electric fields is studied in the unified theoretical approach based on numerical solution of the non-stationary Schrödinger equation. The developed approach implemented in the <em>StarkD</em> software package is free from limitations of perturbation theory. Based on the results of calculations, regularities in the behavior of the energy spectrum, the transition probabilities, and the intensities of the Stark components of the spectral lines of rare gas atoms He, Ne, Ar, and Kr have been established for the first time. These regularities make it possible to identify correctly the emission spectra in alternating electric fields. Additionally, the found regularities allow one to estimate the depletion rate of magnetic sublevels of atoms under changes in the electric field parameters, as well as to analyze the role of the electric field in the processes of quenching the atomic spectral lines and increasing their intensities. Practical applications of the obtained theoretical results are considered.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107155"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143473930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ordered substrate based on gold film over SiO2 microspheres for increasing the sensitivity of the laser-induced breakdown spectroscopy method in the study of nanoparticles","authors":"M.A. Shevchenko ,&nbsp;A.N. Maresev ,&nbsp;M.O. Astafurov ,&nbsp;N.V. Tcherniega ,&nbsp;S.O. Klimonsky ,&nbsp;S.G. Dorofeev ,&nbsp;S.F. Umanskaya ,&nbsp;V.V. Voronova","doi":"10.1016/j.sab.2025.107159","DOIUrl":"10.1016/j.sab.2025.107159","url":null,"abstract":"<div><div>In this work, we present an ordered substrate obtained by the vertical deposition of SiO₂ microspheres coated with a gold layer to increase the sensitivity of the Laser-Induced Breakdown Spectroscopy (LIBS) method for analysis of TiO₂ nanoparticles. Plasmonic-ordered-structure-enhanced-LIBS method (POSELIBS) provides enhancement due to localized surface plasmon resonance of an ordered substrate.</div><div>Using computer modeling, the dependence of the maximum local field amplification on the excitation wavelength and geometric parameters of the substrate was investigated. Conditions close to resonance were selected to obtain the maximum amplification of the LIBS signal. Measurements were performed for off- and near-resonant ordered substrates, which are consistent with the modeling results. Using ordered substrates, an increase in the intensity of Ti emission lines by more than an order of magnitude, as well as a significant increase in signal stability, has been demonstrated. Optimal particle concentrations for the most effective signal enhancement were also determined. The ordered substrate synthesized via described method is a convenient way for LIBS signal resonance enhancement in a wide range of excitation wavelengths.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107159"},"PeriodicalIF":3.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143455003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evaluation of coffee-ring effect of serum and Ag NPs mixture drop stains using laser-induced breakdown spectroscopy mapping","authors":"Xinxin Zhang ,&nbsp;Xiaohui Li ,&nbsp;Xue Chen ,&nbsp;Mengshan Shi ,&nbsp;Tao Ren","doi":"10.1016/j.sab.2025.107158","DOIUrl":"10.1016/j.sab.2025.107158","url":null,"abstract":"<div><div>Nanoparticle-enhanced laser-induced breakdown spectroscopy (NELIBS) has shown great potential in improving the sensitivity of normal LIBS. However, the coffee-ring effect (CRE), often encountered when using the dry droplet method (DDM), may affect the accuracy of NELIBS measurements on bioliquid samples. In this paper, evaluation of the CRE of serum and silver nanoparticle (Ag NPs) mixture drop stains was investigated using LIBS mapping. Serum-Ag NPs mixture was dripped onto normal untreated silicon (Si) substrates for solid-liquid conversion using DDM. A two-dimensional grid scan of the whole drop stain was performed using a 1064 nm pulsed Nd: YAG laser, to generate the false-color distribution images of emitting species. The intensity distribution of the C I 247.86 nm line was used to distinguish the serum drop from the Si substrate, and to distinguish the center and ring regions of the stain. The CRE patterns varied for different emitting species. The distribution images of C, CN, Ca, and Mg emissions showed clear boundaries between the center and the ring regions. However, the K emission concentrated in the center region. The morphological variations of the coffee-rings were related to the mixing volume ratio of serum and Ag NPs. With the increase of Ag NPs, the distribution of emitting species in the center region became more uniform, and the CRE can be mitigated by adjusting the ratio of serum and Ag NPs. The intensities of the center and the ring regions were retrieved and evaluated. The percentage of the center region spectral intensity was more than 60 % relative to the whole drop stain, and gradually increased up to 98 % with the increase of Ag NPs. The variation trend of the spectral intensity of the center region was similar to that of the whole droplet. The enhancement effect of the Ag NPs on the spectral emissions was further investigated. When the volume ratio of serum to Ag NPs was 1:2, the highest enhancement factors for K I 766.49 nm line and Ca II 393.36 nm line were obtained as 2.27 and of 1.90, respectively. This work showed the potential of LIBS mapping in evaluation of the CRE of liquid drop stains. The results could provide important references for LIBS measurements of serum-Ag NPs drop stains on normal untreated solid substrates.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107158"},"PeriodicalIF":3.2,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The investigation of fast hydrogen atoms created in low pressure pulsed discharge in hydrogen-containing gas mixtures by means of Hα line Doppler spectroscopy","authors":"J. Jovović","doi":"10.1016/j.sab.2025.107156","DOIUrl":"10.1016/j.sab.2025.107156","url":null,"abstract":"<div><div>Doppler spectroscopy of the H_α line is used for the study of fast hydrogen atoms created in a novel gas discharge source operating at lower pressure in hydrogen-containing gas mixtures. The discharge is formed around the rod shaped cathode in pulsed high voltage regime with the possibility to change pulse width, duty cycle and electric parameters. The cathodes made of copper, stainless steel, aluminum and graphite are used in the frame of this study. In case of argon carrier gas, the fitting function consisting of two Gaussian profiles is applied and the side-on H_α profiles (observation angle 90° relative to the surface normal) are analyzed in order to measure mean kinetic energy, maximum gained energy and the contribution of fast excited atoms to overall H I profile. The pedestal of the H I line reflects the presence of fast H* atoms in the discharge. From the end-on H I profiles (observation along the surface normal), the maximum H* energy is deduced and compared with the side-on results. The radial distribution of fast H* depicted the linear decrease of mean kinetic energy near the cathode surface as well as the strong dependence of excessive broad component area with gas pressure. In case of H₂, H₂ + 5 % Ar and Ne+0.8 % H₂, the overall fit comprises three Gaussian components. In case of graphite cathode, the mean kinetic energies are 37 eV (Ar + 3 % H₂), 102 eV (H₂ + 5 % Ar), 76 eV (N₂ + 5 % H₂), 167 (Ne+0.8 % H₂) and 180 eV (H₂). The energy of fast H* atoms with the graphite cathode (the maximum voltage not exceeding 750 V) has the lowest value mainly due to low values of energy reflection coefficients. The maximum energy gained in the sheath (∼425 eV) is achieved for the copper cathode and neon‑hydrogen mixture.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107156"},"PeriodicalIF":3.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research on the calorific value detection method and influencing mechanism of solid materials via EDXRF","authors":"Zhi-Hui Zheng ,&nbsp;Yao Shi ,&nbsp;Jun Du ,&nbsp;Hui-Quan Li ,&nbsp;Jing-Jing Shi ,&nbsp;Zhi-Hong Li ,&nbsp;Chen-Mu Zhang","doi":"10.1016/j.sab.2025.107154","DOIUrl":"10.1016/j.sab.2025.107154","url":null,"abstract":"<div><div>Traditionally, calorific value detection has relied on laboratory methods, with a notable lack of rapid techniques for industrial applications. This paper proposes using EDXRF for the quick determination of calorific values, demonstrated through a case study on leaching slag and coke mixtures from zinc smelting. The investigation focuses on detecting calorific values in complex solid materials via X-ray fluorescence, highlighting key factors that influence method stability and accuracy. The results show that (1) Quantitative analysis of calorific values through X-ray fluorescence allows plotting numerical relationships between total spectral count rate, Compton scattering peak intensity (Mo-Ka-C), and Rayleigh scattering peak intensity (Mo-Ka). (2) Factors such as raw material particle size, water content, and instrumental parameters significantly affect detection stability; moisture is particularly critical. As water content increases from dry to 30 wt%, the correlation coefficient between total count and calorific value decreases from 0.8901 to 0.50342. (3) A predictive model correlating Mo–Ka–C intensity with the calorific value of leaching slag mixtures predicts a root mean squared error (RMSEP) of 0.59 MJ/kg and an average relative deviation (ARE) of 4.24 %, indicating improved prediction accuracy for estimating leaching slag's calorific value. The standard deviation (SD) of predicted values was 0.11 MJ/kg, surpassing national standards for repeatability.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107154"},"PeriodicalIF":3.2,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Laser-induced breakdown spectroscopy combined with multi-task convolutional neural network for analyzing Sm, Nd, and Gd elements in uranium polymetallic ore","authors":"Zhuo Wu ,&nbsp;Jian Wu ,&nbsp;Xinyu Guo ,&nbsp;Huihui Zhu ,&nbsp;Yubo Zhang ,&nbsp;Xiaohui Su ,&nbsp;Fuli Chen ,&nbsp;Minghui Li ,&nbsp;Runhui Wang ,&nbsp;Keyi Xu ,&nbsp;Tao Lü","doi":"10.1016/j.sab.2025.107153","DOIUrl":"10.1016/j.sab.2025.107153","url":null,"abstract":"<div><div>When analyzing rare earth elements in uranium polymetallic ores using laser-induced breakdown spectroscopy (LIBS), issues such as spectral interference and overlap significantly reduce the accuracy of elemental analysis. A multi-task convolutional neural network (CNN) model based on an uncertainty-weighted loss function is developed, with raw LIBS spectral data as the input. Conduct experiments using pure oxides under the same experimental conditions to identify the characteristic spectral lines. The results show that, compared to normalized and feature-extracted data processed with partial least squares (PLS), random forests (RF), and single-task CNN models, multi-task CNN model with uncertainty loss achieves the best quantitative results for Sm and Nd elements (Sm: R² = 0.9939, RMSE = 0.6373; Nd: R² = 0.9987, RMSE = 0.3040), and also demonstrates excellent performance in quantifying Gd (R² = 0.9949, RMSE = 0.6106). The multi-task CNN model based on an uncertainty-weighted loss function indicates great potential applications for end-to-end processing of LIBS spectra from uranium polymetallic ore. © 2001 Elsevier Science. All rights reserved.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107153"},"PeriodicalIF":3.2,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}