Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

{"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}

{"title":"Novel insights on the matrix effect of acid solutions in nitrogen microwave-induced plasma optical emission spectrometry: Analytes signal enhancement in formic acid","authors":"Christiane Duyck ,&nbsp;Edmilson Arruda dos Santos ,&nbsp;João Victor Soares de Araújo ,&nbsp;Thiago Silva Santos ,&nbsp;Ricardo Jorgensen Cassella ,&nbsp;Rafaella Regina Alves Peixoto","doi":"10.1016/j.sab.2025.107152","DOIUrl":"10.1016/j.sab.2025.107152","url":null,"abstract":"<div><div>This study evaluated the matrix effect of acid solutions on the nitrogen microwave-induced plasma optical emission spectrometry (N₂-MIP-OES) sensitivity of 24 elements. A model solution of 0.2 % nitric acid was used to compare the element's emission line sensitivity in nitric (1.0 %, and 5.0 %, v v⁻¹), sulfuric (0.2 % and 1 %), hydrochloric, formic, and acetic acid solutions (0.2 %, 1.0 %, and 5.0 %, v v⁻¹). The relative sensitivity was estimated by the linear regression slope (LRS) of signal intensities obtained at eight concentration levels (blank + standards). Principal component analysis (PCA) was applied to the LRS data to distinguish matrix effects. Signal enhancement was noted for a group of elements (Al, As, B, Ba, Cd, Co, Cu, Fe, Mn, Pb, Sr, and Zn) in formic acid solutions (0.2 % and 1 %) and varied from +50 % (Cd, Zn) to +80 % (B, Ba, Pb, Sr) of the corresponding sensitivity in HNO₃ 0.2 %. In contrast, signal suppression occurred for K (−15 %), Ca (−20 %), and Mg (−40 %) and in diluted hydrochloric solutions (0.2 % and 1 %). The ratio values of Mg(II)/Mg(I) and (N₂⁺/OH) used in robustness metrics increased in these solutions, indicating higher robustness. An increase in CO⁺ species formation in the plasma was also observed. Refractory oxide-forming elements (Ce, Cr, La, Mo, Ni, Se, and V) were less impacted by acid matrix effects. This study aimed to contribute to the increasing interest in multi-elemental determination by MIP-OES.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107152"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403560","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":"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)00028-X","DOIUrl":"10.1016/S0584-8547(25)00028-X","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"225 ","pages":"Article 107143"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143378409","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":"Acoustic signal in overcoming the matrix effect in LIBS: Toward reliable applicability","authors":"Markéta Bosáková ,&nbsp;Karel Novotný ,&nbsp;Javier Moros ,&nbsp;Javier Laserna","doi":"10.1016/j.sab.2025.107140","DOIUrl":"10.1016/j.sab.2025.107140","url":null,"abstract":"<div><div>The versatility of laser-induced breakdown spectroscopy (LIBS) resulting from its advantageous analytical characteristics is, unfortunately, still limited by challenges inherent to the fundamental principles of the method – the processes of laser ablation and laser-induced plasma generation. Unwanted effects (generally known as matrix effects) significantly decrease the analytical performance of LIBS, complicating quantification and impairing reproducibility.</div><div>This study investigates acoustic signals accompanying plasmas (LIPAc) to overcome these limitations and enhance LIBS performance. The influence of instrumental (microphone types), operational (laser wavelength and fluence) and sample parameters on acoustic responses were evaluated. The results indicate that laser fluence strongly influences acoustic wave oscillation. When laser fluence substantially exceeds the breakdown thresholds of the different components in the matter, acoustic responses may become identical across various materials. On the other hand, proportionality in differences of acoustic signal is maintained for different microphones and laser wavelength settings.</div><div>Promising solutions for eliminating matrix effects on various surfaces were identified, but the suitability and efficiency may be highly dependent on the emission line used. This is demonstrated using the signals of atomic Cu(I) 324.74 nm and ionic Cu(II) 329.04 nm lines measured from an aluminum sample with a partially coppered and partially roughened surface.</div><div>Acoustic maps of a galena ore sample demonstrate the applications of LIPAc in spatially resolved LIBS imaging and elemental mapping. These maps can help eliminate the discrepancy between the intensities of the calcium atomic line of Ca(I) at 422.67 nm measured from the galena mineral and calcium carbonate.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107140"},"PeriodicalIF":3.2,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387074","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":"Characterization of electron density and ionization of a uranium laser produced plasma using laser absorption spectroscopy","authors":"Ryland G. Wala ,&nbsp;Mathew P. Polek ,&nbsp;Sivanandan S. Harilal ,&nbsp;R. Jason Jones ,&nbsp;Mark C. Phillips","doi":"10.1016/j.sab.2025.107142","DOIUrl":"10.1016/j.sab.2025.107142","url":null,"abstract":"<div><div>High-resolution tunable laser spectroscopy is used to measure time-resolved absorption spectra for ten neutral uranium transitions and six singly-ionized transitions in a laser produced plasma. Spectral lineshapes are analyzed to determine temporal variations in ion and neutral total column densities, excitation temperatures, kinetic temperatures, and collisional broadening effects as the plasma cools. Comparison of ion to neutral column densities shows a ratio greater than 10 at times <span><math><mo>&lt;</mo></math></span>15 μs after plasma onset, with the ratio not reaching unity until 50 μs. Spectral lineshapes are analyzed to separate Stark and van der Waals contributions to collisional broadening, from which electron densities are determined and found to decrease from <span><math><mo>∼</mo></math></span>10¹⁵–10¹³ cm⁻³ over times from 4–25 μs. Using absorption spectroscopy to determine charge properties and electron density over these time scales and at low magnitudes provides valuable insight into plasma properties not obtainable using conventional emission spectroscopy. Comparisons between ion and neutral densities, excitation temperatures, kinetic temperatures, and electron densities could indicate potential deviations from local thermodynamic equilibrium and Saha ionization predictions.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107142"},"PeriodicalIF":3.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487617","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":"Duplication of periodic micro-structure on the surface of a nickel substrate and its application in surface-enhanced laser-induced breakdown spectroscopy","authors":"Zenghui Wang,&nbsp;Yufeng Li,&nbsp;Yuqi Chen,&nbsp;Runhua Li","doi":"10.1016/j.sab.2025.107139","DOIUrl":"10.1016/j.sab.2025.107139","url":null,"abstract":"<div><div>In order to improve the analytical performance of surface-enhanced laser-induced breakdown spectroscopy (SENLIBS) on the elemental analysis of liquid samples, a 20 μm cylindric rod periodic micro-structure with 20 μm rod diameter, 15 μm rod height and 40 μm periodic length was successfully duplicated on the surface of a nickel substrate using electroplating method. The presence of periodic micro-structure on nickel surface changes the interaction of the laser and substrate; thus, plasma with higher temperature and higher electron density can be generated. The atomic emissions of both analytes and substrates' elements can be significantly enhanced in SENLIBS analysis if compared with that of using a flat substrate without any micro-structures. Mn, Pb, and Cr in aqueous solution samples were quantitatively analyzed by SENLIBS using these surface micro-structured nickel substrates. The detection limit of Mn, Pb, and Cr reached to 107.9 ng/mL, 76.0 ng/mL and 70.5 ng/mL under current experimental condition, respectively. In comparison with that obtained in similar analysis using flat nickel substrates, 4.2–5.1 folds improvement factors on the analytical sensitivity were achieved. This approach demonstrates a cost-effective and convenient method for the substrate preparation and provides a more sensitive elemental analysis of liquid samples by SENLIBS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107139"},"PeriodicalIF":3.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143348992","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}