Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

{"title":"U-Pu and Ba-Cs isotopic measurements on Trinitite by laser ablation sampling on the Neoma MC-ICP-MS","authors":"N. Alex Zirakparvar,&nbsp;Toya Beiswenger,&nbsp;Brian Ticknor,&nbsp;Daniel Dunlap,&nbsp;David Glasgow,&nbsp;Matt Darnell,&nbsp;Shalina C. Metzger,&nbsp;Cole R. Hexel,&nbsp;Benjamin T. Manard","doi":"10.1016/j.sab.2025.107334","DOIUrl":"10.1016/j.sab.2025.107334","url":null,"abstract":"<div><div>In this study we present the results of combined U-Pu and Ba-Cs isotope measurements obtained by laser ablation (LA) sampling of two glassy debris fragments (‘Trinitite’) from the world's first atomic bomb detonation conducted in New Mexico on July 16, 1945. Our primary goal in conducting these measurements was to understand whether examination of the U-Pu and Ba-Cs systematics by direct sampling (e.g. without any chemical separation or purification prior to isotope ratio measurement) could yield meaningful information that would differentiate the Trinitite fragments from glassy material lacking a nuclear fission signature. These measurements were conducted on a ThermoFisher Scientific Neoma multi collector – inductively coupled plasma – mass spectrometer (MC-ICP-MS), which is a relatively new MC-ICP-MS platform, so we also examine the behavior of these isotope systems in standards sampled in solution and via LA. Unsurprisingly, the measurements made on purified solutions of the U, Pu, and Ba isotopic standards produce high precision isotope ratios. This extends to the U-Pu measurements made by LA sampling, with the expected degradation in precision and accuracy related to matrix effects and signal intensity fluctuation. However, the Ba-Cs data acquired by LA is of low precision across all of the matrices examined and bears evidence of complex mass fractionation that will require further investigation to resolve. In total, our results indicate that the observed U-Pu isotope data are of sufficient quality to accurately constrain the U and Pu isotopic composition of glass containing sub-ppm levels of these elements which in turn could be used to differentiate glass containing anthropogenic fission products from natural glass whereas the Ba-Cs LA data cannot be used for this purpose until further methodological refinement is performed.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107334"},"PeriodicalIF":3.8,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046408","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":"Influence of ion acceleration on LIBS in reduced-pressure and vacuum environments","authors":"Ding Li,&nbsp;Shibiao Yan,&nbsp;Li Wang,&nbsp;Tianyang Sun,&nbsp;Yunfei Rao,&nbsp;Haoyu Yang,&nbsp;Yucong Jin,&nbsp;Chen Sun,&nbsp;Jin Yu","doi":"10.1016/j.sab.2025.107335","DOIUrl":"10.1016/j.sab.2025.107335","url":null,"abstract":"<div><div>With the important application of LIBS for deep-space exploration, characterizing laser-plasma in reduced-pressure environment, such as on Mars, and in vacuum, such as on Moon and in tokamak, is of vital significance for the optimization of LIBS operation. In these environments, the well-known ion acceleration effect within laser-plasma leads to distinct dynamic characteristics of the plasma as well as the associated LIBS signal. Although the physical process of the ion acceleration effect has been extensively studied in the area of Pulsed Laser Deposition (PLD), its influence on LIBS has not been fully understood. In this work, we investigated the impact of ion acceleration on the characteristics of laser-induced titanium plasma in these environments by using fast imaging and spatiotemporally resolved spectroscopy. It can be found that in a reduced-pressure environment, a diminished resistance of the ambient gas enables ions in different charge states to dominate among different components of a plasma with a split two-component structure during its early stage of expansion. As these components expand and interact, a plasma with a homogeneous spatial distribution of Ti I and Ti II forms at a delay of 1000 ns, characterized by an emission with high signal-to-noise ratio (SNR) and signal-to-background ratio (SBR). This indicates an optimal time window for LIBS measurements in a reduced-pressure environment at this time stage. In the entire absence of ambient gas as in vacuum environment, the lack of the background gas resistance allows the ions in highly charge state to be accelerated freely in the ambipolar electric field, resulting in the severe shortening of the plasma duration. On the other hand, a stronger ion acceleration facilitates highly charged ions, such as Ti IV, to expand and predominate at the plume front during the early stage of plasma expansion, when continuum background is rather lower. As a result, the SBR of Ti IV is several times higher than that of the other lines. Considering the species segregation caused by ion acceleration, the local thermodynamic equilibrium (LTE) for titanium atoms and ions in different charge states are evaluated based on temperature and electron density of the plasmas induced in different environments. The results indicate that the transient nature of Ti III and Ti IV conducts them to deviate from LTE during the early stage of plasma expansion, while Ti I and Ti II remain in LTE throughout the investigated delays. These results offer insights into the characteristics of laser-induced plasma in reduced-pressure and vacuum environments, helping therefore the application of LIBS in deep-space exploration.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107335"},"PeriodicalIF":3.8,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106465","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":"Effect of humidity on LIBS measurement of premixed methane–air equivalence ratio","authors":"Michaela R. Hemming,&nbsp;Kunning G. Xu","doi":"10.1016/j.sab.2025.107322","DOIUrl":"10.1016/j.sab.2025.107322","url":null,"abstract":"<div><div>The scope of this work is to quantify the impact of ambient air conditions on the laser-induced breakdown spectroscopy (LIBS) analysis of injector flow of premixed methane and air. The tracked species in the LIBS spectra are the Balmer series hydrogen-alpha emitting light at a wavelength of 656.3 nm and an oxygen triplet emitting at 777.4 nm. The ratio of <span><math><mrow><msub><mrow><mi>H</mi></mrow><mrow><mi>α</mi></mrow></msub><mo>/</mo><mi>O</mi></mrow></math></span> is used to determine not only the equivalence ratio of the premixed propellants but also the concentration of water in stagnant air. The experimental results of the humidity are validated through Boltzmann intensity ratio relationships and simulated spectra using PrismSPECT and used to correct the gas-flow species concentrations. The results show that, for every 10% increase in relative humidity, the corrected <span><math><mrow><msub><mrow><mi>H</mi></mrow><mrow><mi>α</mi></mrow></msub><mo>/</mo><mi>O</mi></mrow></math></span> ratio will decrease by approximately 6%.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107322"},"PeriodicalIF":3.8,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046407","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":"Applicability of liquid-liquid extraction to increase sensitivity of determination of fourth period transition metals in iron ores by total-reflection X-ray fluorescence analysis","authors":"Alena N. Zhilicheva ,&nbsp;Galina V. Pashkova ,&nbsp;Artem S. Maltsev","doi":"10.1016/j.sab.2025.107333","DOIUrl":"10.1016/j.sab.2025.107333","url":null,"abstract":"<div><div>The presence of intensive X-ray fluorescence of iron as well as escape peaks in the spectrum of geochemical samples has a negative impact on direct quantification of low amounts of neighboring elements. In this paper, using the analysis of iron ores as a case study, it is shown that removal of the iron matrix by liquid-liquid extraction improves the sensitivity and accuracy of determination of fourth-period transition metals (Ti, V, Cr, Mn, Co, Ni, Cu, Zn) compared to direct suspension analysis. A procedure involved acid digestion of ore powder by aqua regia, Fe removing with methyl isobutyl ketone from hydrochloric acid medium, TXRF measurement of aqueous phase containing Ga as an internal standard. Intralaboratory precision calculated using duplicate sample preparations ranged from 1 to 9 % for all considered elements. After extraction of iron, it became possible to determine Co, V, Cr and Ni which weren't detected in iron ore samples using direct analysis. However, for some samples, determination of Cr can be considered only as semi-quantitative because minerals containing Cr did not fully dissolve during acid decomposition.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107333"},"PeriodicalIF":3.8,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046409","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)00209-5","DOIUrl":"10.1016/S0584-8547(25)00209-5","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107324"},"PeriodicalIF":3.8,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144996255","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 determination of germanium by hydride generation-atmospheric pressure glow discharge optical emission spectrometry (HG-APGD OES)","authors":"Tymoteusz Kliś ,&nbsp;Piotr Jamróz ,&nbsp;Jan Kratzer ,&nbsp;Krzysztof Gręda ,&nbsp;Paweł Pohl","doi":"10.1016/j.sab.2025.107323","DOIUrl":"10.1016/j.sab.2025.107323","url":null,"abstract":"<div><div>Hydride generation (HG) was combined with an atmospheric pressure glow discharge (APGD) to determine Ge by optical emission spectrometry (OES) employing the Ge I 265.1 nm emission line. It was revealed that efficient atomization of GeH₄ and excitation of Ge atoms require a microplasma with a higher energy density than other hydride-forming elements such as As, Sb, and Se. The operating conditions were optimized: discharge gap = 0.5 mm, cathode nozzle diameter = 0.7 mm, current = 45 mA, and carrier/discharge gas flow rate of 400 mL min⁻¹ He. The measurement repeatability (<em>n</em> = 10) was within the range of 3.3–4.8 %, demonstrating the high stability of the novel HG-APGD system. The upper limit of linearity was 1000 μg L⁻¹ Ge, and the method was resistant to interferences from easily ionized elements (Ca, K, Mg) at concentrations up to at least 100 mg L⁻¹. The detection limit (DL) of Ge (0.4 μg L⁻¹) was comparable to the values achieved using more expensive and sophisticated analytical instrumentation based on inductively coupled plasma (ICP) or microwave induced plasma (MIP) combined with OES. The trueness of HG-APGD OES was confirmed through a recovery test, which showed a high agreement between spiked and measured concentrations of Ge in the matrix of bottled, mineral-rich, river, and tap water samples. The Ge recoveries ranged from 99 % to 114 % at the spiking concentration of 10–20 μg L⁻¹.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107323"},"PeriodicalIF":3.8,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020422","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":"Analytical comparison between standard and micro sample flow rate for the dilute-and-shoot analysis of glycerin samples by ICP OES","authors":"Marina Araujo João Lopes da Costa ,&nbsp;Patrícia Viana Rodrigues ,&nbsp;Aderval S. Luna ,&nbsp;Fernanda Nunes Ferreira ,&nbsp;Jefferson Santos de Gois","doi":"10.1016/j.sab.2025.107319","DOIUrl":"10.1016/j.sab.2025.107319","url":null,"abstract":"<div><div>In this study, standard and micro sample flow rates (using the same nebulizer) were systematically investigated for the “dilute-and-shoot” determination of As, Ca, Cu, K, Mg, Na, P, Pb, and Zn in glycerin samples using inductively coupled plasma optical emission spectrometry (ICP-OES). The presence of glycerin affected the element determination by ICP-OES using lateral and axial views; the interferences could not be corrected with internal standards, regardless of the sample flow rates. The best selection of instrumental conditions for the trace-element determination in glycerin samples involved simple dilution of glycerin samples in HNO₃ 0.14 mol L⁻¹, followed by matrix-matching calibration and using Sc as an internal standard. The limits of detection were, in μg g⁻¹, 0.1 (As), 0.03 (Ca), 0.007 (Cu), 0.005 (K), 0.003 (Mg), 0.004 (Na), 0.2 (P), 0.1 (Pb) and 0.01 (Zn), while the short-term precision was lower 2.0 % for most analytes. Three samples of commercial glycerin were analyzed, and the method provided a robust and reliable approach for accurately quantifying impurities in glycerin, ensuring regulatory compliance and suitability for various industrial applications.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107319"},"PeriodicalIF":3.8,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933862","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":"Experimental stark broadening parameters of Bi I, Bi II and Bi III spectral lines in laser-induced plasma","authors":"Nikodin V. Nedić,&nbsp;Dejan Dojić,&nbsp;Miloš Skočić,&nbsp;Srdjan Bukvić","doi":"10.1016/j.sab.2025.107321","DOIUrl":"10.1016/j.sab.2025.107321","url":null,"abstract":"<div><div>We present experimentally determined Stark width parameters (<em>w</em> - Full Width at Half Maximum) for 5 neutral (Bi I), 13 singly (Bi II), and 3 doubly ionized (Bi III) bismuth atoms spectral lines in the wavelength range of 298 to 570 nm. The experiment was conducted with a Laser-Induced Plasma (LIP) in helium gas at reduced pressure, as a source of spectra recorded in side-on geometry. Plasma parameters were estimated after applying the inverse Abel transform to the laterally resolved LIP profiles. The widths and relative intensities of all selected bismuth spectral lines were determined by their fit to the Voigt function. Electron number density values, on different plasma radial positions, were estimated in the range of (0.3–1.1) × 10²³ m⁻³ based on the Stark broadening of the well-established diagnostic He I 587.56 nm spectral line. The electron temperature was determined using the Saha-Boltzmann method. Bismuth spectral lines were used to construct a Saha-Boltzmann plot for three consecutive ionization states of bismuth atoms, assuming Local Thermodynamic Equilibrium (LTE) in the LIP. These methods for determining electron number density and electron temperature enabled precise estimation of plasma parameters, and therefore also supported the accurate determination of the newly measured Stark width values of bismuth spectral lines. The experimental measurements in this study provided the first-ever data on Stark widths for selected specific bismuth spectral lines, not previously available according to the NIST database, which are suitable for further plasma diagnostics, astrophysical modeling, and the development of spectroscopic techniques in laboratory and industrial applications. We also discussed a well-known feature of bismuth, the hyperfine structure of spectral lines due to nuclear spin and associated magnetic moment.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107321"},"PeriodicalIF":3.8,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144932354","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":"Surveying the acoustics from laser-induced plasmas under non-standard atmospheric conditions: Implications for extraterrestrial missions","authors":"Markéta Bosáková ,&nbsp;Javier Moros ,&nbsp;José M. Vadillo ,&nbsp;Karel Novotný ,&nbsp;J. Javier Laserna","doi":"10.1016/j.sab.2025.107320","DOIUrl":"10.1016/j.sab.2025.107320","url":null,"abstract":"<div><div>The snapping sound accompanying laser produced plasmas are standing out in recent times as a complementary source of information to the spectroscopic measurements, allowing to catalogue occurring processes as well as to categorize inspected samples. These promising uses are currently considered for the identification of geological material and the characterization of the Martian atmosphere by the SuperCam instrument and its microphone onboard the NASA Perseverance rover. The singularity of each laser plasma, combined with the effect of the different atmospheric environments in which its expansion can occur (composition, pressure, temperature, etc.) provides multiple scenarios that affect the analytical signals generated. Despite the extensive bibliography on the effects of the surrounding atmosphere on the optical emission of laser-induced plasmas, little has been studied about the acoustics derived out of them. The present work aims to systematically scrutinize the effect of the more common atmospheric variables like pressure, temperature and composition into the final acoustic signal from laser-induced plasmas to accurately use this information source.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107320"},"PeriodicalIF":3.8,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933797","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":"Comparing LIBS of marine coatings using femtosecond pulses and continuous wave laser cleaning","authors":"Doyinsola S. Sonoiki ,&nbsp;Coraline Lapre ,&nbsp;Morten Schnohr ,&nbsp;Kim Scheibel ,&nbsp;Ole Bang ,&nbsp;Christian R. Petersen","doi":"10.1016/j.sab.2025.107317","DOIUrl":"10.1016/j.sab.2025.107317","url":null,"abstract":"<div><div>This study investigates the laser removal process of marine protective coatings using laser-induced breakdown spectroscopy (LIBS). A high pulse repetition rate femtosecond laser system is first employed in a controlled laboratory setting to examine how different coating samples and laser parameters influence the LIBS signal. By systematically varying these parameters and repeatedly scanning the laser beam in a line across the samples, distinct coating layers are identified based on their spectral signatures. Additionally, the ablation process is analyzed to track the total ablation time required to remove each coating layer. The LIBS spectra obtained from the fs laser system are then compared with those from a high-power continuous wave laser system designed for industrial coating removal. The comparison highlights key differences in plasma formation, spectral characteristics, and signal quality between the two systems. These findings enhance the understanding of how laser parameters influence plasma generation and emission spectra during coating ablation, providing insights that could optimize LIBS-based elemental analysis for improved process monitoring and selective coating removal in industrial applications.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107317"},"PeriodicalIF":3.8,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933923","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}