Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

{"title":"LIBS signal enhancement by laser surface microstructuring of copper","authors":"Alexandre Cherrier,&nbsp;Lionel Canioni,&nbsp;Bruno Bousquet","doi":"10.1016/j.sab.2025.107318","DOIUrl":"10.1016/j.sab.2025.107318","url":null,"abstract":"<div><div>This paper describes the optimization of femtosecond laser surface microstructuring of copper to obtain LIBS signal enhancement. Microstructures in the form of periodic rows are created on a copper sample with depths between 2 μm and 24 μm by tuning the femtosecond laser power, frequency, as well as the translation stage speed. A darkening effect is observed in the zones with microstructures, corresponding to a better light trapping effect than on a polished surface. The LIBS signal enhancement of the Cu I line at 521.8 nm is used as an indicator to select the type of microstructures which induces the maximum enhancement of the plasma emission. Characterizations of the microstructures through confocal microscopy and Time of Flight Secondary Ion Spectrometry are used to explain the change in signal enhancement between different microstructures. More specifically, deeper and darker microstructures are shown to provide less signal enhancement due to the higher content of copper oxide within the typical LIBS crater depth. A signal enhancement as high as 11 is obtained on the optimized microstructure. This enhancement is the result of a 70 % increase in electron density, 17 % increase in temperature and two times higher plasma lifetime. Finally, the resulting microstructured copper sample is used as a substrate for the LIBS analysis of a liquid. In this study, mineral water is dropped and dried on the substrate, and the LIBS signal of the Ca I lines intensities at 526.2 nm, 526.5 nm and 527.0 nm is found to be roughly four times higher than on the copper substrate without microstructures.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107318"},"PeriodicalIF":3.8,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144926760","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":"Determination of calcium in gadolinium-based contrast agents using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) in the cool plasma/N2O reaction mode","authors":"Biyu Ni ,&nbsp;Chao Zheng ,&nbsp;Jianhua Huang ,&nbsp;Lin Chen ,&nbsp;Wen Xie","doi":"10.1016/j.sab.2025.107316","DOIUrl":"10.1016/j.sab.2025.107316","url":null,"abstract":"<div><div>Calcium (Ca), as an impurity, can affect the efficacy and safety of gadolinium-based contrast agents (GBCAs) through ligand competition, precipitation formation, or biological interference. To meet the requirements of GBCA analysis and testing and ensure the quality and safety of GBCAs, a novel strategy was proposed to determine Ca content in GBCAs using inductively coupled plasma tandem mass spectrometry (ICP-MS)/MS. The sample was directly analyzed using ICP-MS/MS after dilution with 2 % nitric acid. Under cool plasma conditions, the formation of ⁴⁰Ar⁺ was reduced by inhibiting the ionization of the plasma gas Ar at low temperatures. In the MS/MS mode, with N₂O as the reaction gas, and based on the case that ⁴⁰Ca¹⁶O⁺ was generated through the O-atom transfer reaction between ⁴⁰Ca⁺ and N₂O (⁴⁰Ca⁺ + N₂O → ⁴⁰Ca¹⁶O⁺ + N₂) and that other interfering ions did not undergo the mass shift reaction with N₂O, spectral interference was eliminated using the mass shift method. The accuracy, reliability, and precision of the method were evaluated by analyzing standard reference materials (NIST SRM 1640a and NIST SRM 1643f) and performing spike recovery. The limit of detection (LOD) of Ca was as low as 1.35 ng L⁻¹ (obtained for ⁴⁰Ca), the relative standard deviation was 1.8 %–2.7 %, and the spike recovery was 98.6 %–102 %. Thus, a systematic method was established using ICP-MS/MS to accurately quantify the challenging element Ca in GBCAs and to highlight its potential in other fields.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107316"},"PeriodicalIF":3.8,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144916547","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":"Enhancing laser ablation inductively coupled plasma mass spectrometry analysis through empirical modeling of crater geometry","authors":"Antea Hrepić ,&nbsp;Filip Cernatič ,&nbsp;Kristina Mervič ,&nbsp;Sanda Rončević ,&nbsp;Ivan Nemet ,&nbsp;Martin Šala","doi":"10.1016/j.sab.2025.107305","DOIUrl":"10.1016/j.sab.2025.107305","url":null,"abstract":"<div><div>Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) systems are engineered to produce uniform, flat-top beam profiles for optimal surface sampling. In practice, however, rounder beam profiles are prevalent. Their geometrical characteristics can be mathematically described using the two-dimensional super-Gaussian or even a Gaussian function for smaller beam sizes, with the super-Gaussian factor (<em>n</em>) serving as a quantifier. Since the beam profile and the ablation grid have a direct influence on the amount of sampled surface material, the idea is to reduce the ablation grid by sub-pixel mapping to improve the accuracy of surface scanning, increase pixel density, improve spatial resolution, and increase signal-to-noise ratio (SNR). This paper explores the relationship between super-Gaussian order (<em>n</em>), beam size, and laser fluence for circular beams, using two laser ablation systems with different wavelengths – 193 nm and 213 nm nanosecond lasers. An empirical model was developed to yield the factor <em>n</em>, facilitating the determination of the contraction factor (<em>k</em>). Identifying the precise contraction factor for each beam size brings the beam profile closer to a flat-top shape, producing smoother post-ablation surfaces and enhancing image quality due to heightened pixel density. Ultimately, such models improve our understanding of crater geometry optimization, leading to better analytical outcomes in LA-ICP-MS analysis.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107305"},"PeriodicalIF":3.8,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913007","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 determination of the sodium K-shell atomic fundamental parameters for X-ray spectroscopy","authors":"Marie-Louis Venzke ,&nbsp;Katja Frenzel ,&nbsp;Pouya Partovi-Azar ,&nbsp;Philipp Hönicke","doi":"10.1016/j.sab.2025.107303","DOIUrl":"10.1016/j.sab.2025.107303","url":null,"abstract":"<div><div>Reliable fundamental parameters are essential for accurate X-ray fluorescence analysis of sodium. This work presents updated experimental values with reliable uncertainties for sodium K-shell fundamental parameters such as: fluorescence yield, photoionization cross sections, and Auger yields. Using a physically calibrated setup and a thin NaCl layer on a silicon nitride membrane, a holistic determination approach was applied to reduce uncertainties. The new values represent a significant improvement on the ones widely used in databases. All data are available via Zenodo to support precise sodium quantification in scientific and industrial applications.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107303"},"PeriodicalIF":3.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144907205","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":"Doublet line ratio-based self-absorption correction in LIBS applied to bacterial concentration quantification","authors":"Fei Chen ,&nbsp;Jiahui Liang ,&nbsp;Shuqing Wang ,&nbsp;Zhihui Tian ,&nbsp;Yang Zhao ,&nbsp;Yan Zhang ,&nbsp;Lei Zhang ,&nbsp;Wangbao Yin ,&nbsp;Jiaxuan Li ,&nbsp;Peihua Zhang ,&nbsp;Liantuan Xiao ,&nbsp;Suotang Jia","doi":"10.1016/j.sab.2025.107314","DOIUrl":"10.1016/j.sab.2025.107314","url":null,"abstract":"<div><div>Laser-induced breakdown spectroscopy (LIBS) is widely recognized for its rapid, low-destructive, and real-time elemental analysis capabilities. However, the complexity of bacterial samples and spectral signal interference caused by self-absorption effects present significant challenges to the accuracy and reliability of LIBS for quantitative bacterial concentration analysis. To address these challenges, a novel self-absorption correction method based on doublet line intensity ratios and K-parameter ratios is proposed and, for the first time, successfully applied to improve the accuracy of bacterial concentration quantification. Laser parameters were optimized to verify that the bacterial laser-induced plasma satisfies local thermodynamic equilibrium (LTE). Characteristic doublet lines sharing similar or identical upper and/or lower energy levels (Ca II 393.36/396.84 nm, Ca I 612.22/616.22 nm, and K I 766.49/769.90 nm) were selected to develop a model correlating the K-parameter ratio with the self-absorption coefficient (SA), enabling effective spectral line self-absorption correction. The results show that after self-absorption correction, the quantitative analysis errors were significantly reduced: for <em>Escherichia coli</em> and <em>Bacillus subtilis</em>, the errors decreased by 4.0 % and 11.6 % using Ca II 393.36 nm, 9.1 % and 6.9 % using K I 766.49 nm, and 4.3 % and 3.9 % using Ca I 612.22 nm, respectively. Accurate quantification was achieved within the bacterial concentration range of 10⁷ to 10⁸ CFU/mL. This correction method is straightforward, efficient, and independent of complex parameters or external conditions, significantly improving the precision and reproducibility of LIBS in bacterial concentration analysis. Additionally, the SVM-based classification accuracy for the five bacterial species improved markedly, rising by 3.55 %. Its robust generalizability supports its extension to other microbial detection applications, providing a rapid, accurate, and cost-effective approach. These findings lay a solid foundation for broader LIBS applications in biological monitoring, with promising potential in environmental surveillance, food safety, and public health diagnostics.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107314"},"PeriodicalIF":3.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933796","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":"Application of deep learning methods to LIBS imaging data","authors":"Javier E. Rinaldi,&nbsp;Andrés Lucía,&nbsp;Carlos Ararat-Ibarguen,&nbsp;C.A. Rinaldi","doi":"10.1016/j.sab.2025.107315","DOIUrl":"10.1016/j.sab.2025.107315","url":null,"abstract":"<div><div>This study explores the application of Convolutional Neural Networks (CNNs) to analyze LIBS images for elemental identification in materials such as steel, zirconium, and aluminum. A ResNet-50 architecture was implemented alongside entropy-based preprocessing to enhance feature extraction. The results demonstrate that CNNs efficiently extract complex features and serve as a cost-effective alternative to conventional spectrometric instruments.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107315"},"PeriodicalIF":3.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144932353","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 the self-reversal phenomenon of Ag resonant lines in laser-induced breakdown spectroscopy experiments","authors":"G. Molina-Granados ,&nbsp;C. Sanchez-Aké ,&nbsp;M. Villagrán-Muniz ,&nbsp;F. Bredice ,&nbsp;S. Legnaioli ,&nbsp;V. Palleschi","doi":"10.1016/j.sab.2025.107304","DOIUrl":"10.1016/j.sab.2025.107304","url":null,"abstract":"<div><div>In this work, we analyzed the phenomenon of self-reversal (SR) of spectral lines in Laser-Induced Breakdown Spectroscopy (LIBS) spectra through the study of the temporal evolution of self-reversed emission lines in neutral and ionized silver, using different laser energies and lens-to-target distances.</div><div>In these experiments, the characteristic dip of self-reversed lines corresponding to resonant transitions begins to form on the bremsstrahlung continuum within 20 ns after the laser-induced breakdown. The dip generated in the initial moments presents an inverted Lorentzian shape and, at later times, gradually acquires a Gaussian profile.</div><div>Additionally, we found that the self-reversal phenomenon in silver can occur in all transitions whose lower levels are below 6 eV and whose transition probabilities exceed 10⁸ s⁻¹. The SR depends weakly on the laser pulse energy but is strongly influenced by the lens-to-target distance. It is possible to minimize the effect by adjusting this distance. The formation of craters on the target also favors the appearance of self-reversal.</div><div>We propose a model to explain all the observed characteristics of the self-reversal phenomenon in this work, based on the interaction of Ag atoms and ions ejected by the plasma with the shock wave generated during the breakdown process.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107304"},"PeriodicalIF":3.8,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144916546","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":"Multi-order moment fusion of laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy for mineral classification","authors":"Yao Li ,&nbsp;Zexuan Dong ,&nbsp;Nan Ma ,&nbsp;Yuanbin Wang ,&nbsp;Minchao Cui ,&nbsp;Ming Luo","doi":"10.1016/j.sab.2025.107302","DOIUrl":"10.1016/j.sab.2025.107302","url":null,"abstract":"<div><div>Traditional laser-induced breakdown spectroscopy (LIBS) methods rely primarily on spectral intensity, overlooking the rich statistical information embedded in higher-order moment features such as mean, variance, skewness, and kurtosis. This limitation hinders both the accuracy and generalizability of LIBS in analyzing complex mineral samples. To address this challenge, we introduce a novel approach that extracts and integrates multi-order moment features to enhance spectral representation and improve classification performance. Specifically, we compute higher-order statistical moments from LIBS spectra and standardize them using <em>Z</em>-score normalization to eliminate dimensional bias. A random forest model is then used to assign feature importance weights, guiding the feature fusion process. The resulting LIBS features are further fused at the feature level with Raman spectral data, allowing for multi-parameter representation of each sample. A neural network classifier is subsequently employed to evaluate the model's performance. Experimental results demonstrate that our fusion-based method achieves classification accuracy, precision, and specificity exceeding 99 %, significantly outperforming conventional LIBS-based approaches, which attain only 83.11 % accuracy. These findings highlight the effectiveness of multi-order moment fusion in enhancing spectral analysis of complex samples, and demonstrate its broad potential for applications in mineral identification and beyond.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107302"},"PeriodicalIF":3.8,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144895478","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)00177-6","DOIUrl":"10.1016/S0584-8547(25)00177-6","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"232 ","pages":"Article 107292"},"PeriodicalIF":3.8,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144809539","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":"Method for elemental analysis of iron meteorite by total-reflection X-ray fluorescence (TXRF) spectrometry: novel application to Sikhote-Alin meteorite","authors":"Artem S. Maltsev ,&nbsp;Alena N. Zhilicheva ,&nbsp;Galina V. Pashkova ,&nbsp;Kseniya A. Konovalova","doi":"10.1016/j.sab.2025.107301","DOIUrl":"10.1016/j.sab.2025.107301","url":null,"abstract":"<div><div>Classification of iron meteorites is based on their structure and elemental composition. The chemical composition classification is based, especially on Ni, Ga, Ge, Co, Au and Ir mass fractions and divides iron meteorites into 13 groups. In this work, the potential of elemental analysis of iron meteorites using the TXRF method is explored. In the absence of certified reference materials for iron meteorites, the Sikhote-Alin meteorite was chosen for methodological research due to its high degree of homogeneity in elemental composition. The TXRF method was developed for the determination of Fe, Ni, Ga, and Ge following 6 M nitric acid decomposition and a standardless quantification approach. Liquid-liquid extraction with MIBK was employed to remove Fe from the matrix, and Co and Cu were also determined. The precision did not exceed 4 % for Fe, Ni, Cu, and Ge, 8 % for Co, and 11 % for Ga. The trueness, based on recovery values, was generally in the range of 90–110 % for all elements. The TXRF method enabled detection at the first microgram per gram (μg/g) levels and was considered satisfactory for most types of iron meteorites.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"233 ","pages":"Article 107301"},"PeriodicalIF":3.8,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144828942","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}