Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

{"title":"High-precision Rb-Sr isotope analysis with Neoma MS/MS: Enhancing in situ geochronology by laser ablation","authors":"Chao Huang ,&nbsp;Hao Wang ,&nbsp;Liewen Xie ,&nbsp;Lei Xu ,&nbsp;Shitou Wu ,&nbsp;Yueheng Yang ,&nbsp;Jinhui Yang","doi":"10.1016/j.sab.2025.107117","DOIUrl":"10.1016/j.sab.2025.107117","url":null,"abstract":"<div><div>The development of multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) with tandem mass spectrometry (MS/MS) technology has brought significant advancements for <em>in situ</em> Rubidium‑strontium (Rb-Sr) geochronology, coupled with a laser ablation system (LA). This study investigates the potential of high-precision <em>in situ</em> Rb-Sr dating by the Neoma MS/MS instrument, using both solution and LA analysis, with a focus on optimizing instrumental parameters and the evaluating reference materials. We systematically assess the removal of Ar⁺, the influence of Focus Lens 2 voltage on Sr isotope analytical accuracy, and the effectiveness of reaction mode in eliminating isobaric interferences. Results of LA analyses demonstrate the capability of Neoma MS/MS to achieve high-precision <em>in situ</em> Rb-Sr isotope ratio measurements, with external precisions better than 1.9 % and 0.036 % relative standard deviation (RSD) for ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr ratios in standard glasses, respectively. The homogeneity of the Mica-Mg reference material is further assessed, with an inter-session RSD of 0.17 % for its Rb-Sr isochron age, demonstrating good age homogeneity across nine analytical sessions. Similarly, the natural ZMT04 muscovite yielded an inter-session RSD of 0.69 % for its Rb-Sr isochron age, and its Rb-Sr isochron age of 1778.8 ± 4.9 Ma (2 s, <em>n</em> = 180) is consistent with the reported Ar-Ar age (1772.2 ± 2.7 Ma, 2 s) within the uncertainty, confirming its suitability as a monitor reference material for Rb-Sr dating. These findings highlight the potential of the Neoma MS/MS in enhancing the precision of <em>in situ</em> Rb-Sr dating, for micro-scale investigations and revealing intricate age zonation patterns within individual minerals.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107117"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103866","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":"Multimodal elemental analysis: A unique tool for the provenance of radiolarite artefacts","authors":"Filip Gregar ,&nbsp;Martin Moník ,&nbsp;Petr Hamrozi ,&nbsp;Jitka Součková ,&nbsp;Zdeňka Nerudová ,&nbsp;Tomáš Pluháček","doi":"10.1016/j.sab.2024.107111","DOIUrl":"10.1016/j.sab.2024.107111","url":null,"abstract":"<div><div>Tracing the provenance of lithic artefacts to reconstruct the movements, territories, and social relations of Palaeolithic hunter-gatherers is an important part of modern archaeometry. To estimate the provenance of radiolarites, a type of fine-grained silica rocks, we have developed and validated a multimodal statistical approach consisting of visual examination and elemental analysis. The determination of main and trace elements with portable X-ray fluorescence (pXRF) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allowed us to separate Central European radiolarites into one of three groups of close geographical proximity or, using LA-ICP-MS and multimodal approach, into six groups, ranging from the Northern Calcareous Alps to the eastern edge of the Pieniny Klippen Belt. It emerged that the ten analysed radiolarite artefacts collected at the Nová Dědina I Aurignacian site originated from the Slovak-Polish region, thus confirming the hypothesis that Moravian (Czech Republic) Upper Palaeolithic hunter-gatherers periodically moved towards the mountainous Pieniny Klippen Belt area.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107111"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094320","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":"Dielectric silica NPs for nanoparticle-enhanced laser-induced breakdown spectroscopy: Improving the cobalt element spectral intensity","authors":"Zexuan Wang,&nbsp;Pengji Ding,&nbsp;Shengxian Han,&nbsp;Shan Xue,&nbsp;Zuoming Zhu,&nbsp;Zuoye Liu,&nbsp;Bitao Hu,&nbsp;Shaohua Sun","doi":"10.1016/j.sab.2024.107086","DOIUrl":"10.1016/j.sab.2024.107086","url":null,"abstract":"<div><div>We investigated the enhancement of cobalt spectral using nanoparticle-enhanced laser-induced breakdown spectroscopy (NELIBS) through the utilisation of silica nanoparticles (NPs) with excellent sphericity. The exceptional sphericity of the silica NPs guaranteed stable and consistent experimental results. The spectral intensity of Co as a function of the concentration and the size of silica NPs was explored. Numerical simulations reveal that the abnormal trend of the Co spectral against NPs size is mainly attributed to the local electric field enhancement effect and the adsorption capacity of the silica NPs. Moreover, the silica NPs exhibited excellent dispersion in a mixed solution of ethanol and ultrapure water, resulting in a reduced drying time of approximately one minute. This facilitated the efficient and practical application of silica NPs in NELIBS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107086"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094311","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)00010-2","DOIUrl":"10.1016/S0584-8547(25)00010-2","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107125"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094305","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":"Quantitative analysis of soda-lime glass by the LIBS technique based on the TEA CO2 laser","authors":"Aleksandra Šajić ,&nbsp;Dragan Ranković ,&nbsp;Miroslav Ristić ,&nbsp;Milica Marković ,&nbsp;Jovan Ciganović ,&nbsp;Miroslav Kuzmanović","doi":"10.1016/j.sab.2024.107113","DOIUrl":"10.1016/j.sab.2024.107113","url":null,"abstract":"<div><div>The present work studies the capability of a Laser-Induced Breakdown Spectroscopy (LIBS) system based on a Transversely Excited Atmospheric pressure (TEA) CO₂ laser for quantitative analysis of soda-lime glass. Calibration curves of Cd, Co, Cr and Cu were constructed using the ratio of the analyte emission line intensity to the line intensity of the internal standard. Coefficients of determination <span><math><mfenced><msup><mi>R</mi><mn>2</mn></msup></mfenced></math></span> were in the range from 0.969 to 0.983, depending on the element. The accuracy of LIBS results was confirmed by X-ray spectrometry (XRF). Limits of detection (LODs) for several elements (Cd, Co, Cr, Cu, Fe, Ti and Ca) were estimated (typical values in range of 13‐24 ppm were obtained). The Stark-broadening and two ionic lines intensity ratio were used to determine electron number density and excitation temperature. Profilometric measurements showed the low destructiveness typical for LIBS technique, without glass damage such as shattering and cracking.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107113"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103861","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":"Selected transition probabilities in singly ionized bismuth atoms","authors":"Dejan Dojić,&nbsp;Nikodin V. Nedić,&nbsp;Miloš Skočić,&nbsp;Srdjan Bukvić","doi":"10.1016/j.sab.2024.107114","DOIUrl":"10.1016/j.sab.2024.107114","url":null,"abstract":"<div><div>This paper contains experimentally determined values for the spontaneous emission transition probabilities (Einstein's coefficient <span><math><mi>A</mi></math></span>) of 9 seleced transitions in singly ionized bismuth atoms (Bi II). Laser-Induced Plasma (LIP) was used as a source of the optical emission spectra. Due to LIP spatial inhomogeneity, the inverse Abel transform method was applied to lateral LIP profiles recorded in side-on geometry. The relative intensities of spectral lines were measured as the area under a spectral line profile curve fitted to the Voigt function. The Saha-Boltzmann plot of three consecutive ionization states from Bi spectra was constructed assuming Local Thermodynamic Equilibrium (LTE) in LIP and served for electron temperature estimation. The electron density was estimated based on the Stark width measurement of a well-investigated diagnostic He I 388.86 nm spectral line. The Saha-Boltzmann fit parameters were used for deducing the <span><math><mi>A</mi></math></span> values. The uncertainties for every value of <span><math><mi>A</mi></math></span> were obtained through the error propagation procedure of errors in measured quantities as well as the Monte Carlo method.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107114"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103863","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":"Heavy metal galvanic displacement reaction on micrometer particles to assist LIBS for cu and Cr in liquids analysis with sub μg/L sensitivity","authors":"Hua Liu ,&nbsp;Shenghan You ,&nbsp;Shuaiyu Wu ,&nbsp;Jiamin Li ,&nbsp;Kezeng Pan ,&nbsp;Yiping Wang ,&nbsp;Changhong Zhang ,&nbsp;Lin Zhu ,&nbsp;Shilei Zhong","doi":"10.1016/j.sab.2025.107116","DOIUrl":"10.1016/j.sab.2025.107116","url":null,"abstract":"<div><div>Due to the severe threat posed by heavy metals to human health, relevant authoritative standards impose strict limits on the concentration of metal elements in water bodies, with the allowed minimum concentration of these elements reaching the μg/L level. Therefore, there is an urgent need to develop detection technologies for rapid, multi-element qualitative and quantitative analysis of heavy metal elements in water bodies at the μg/L level, especially in fields such as water quality monitoring or discharge control. This paper proposes a novel approach that combines a micron-sized particle galvanic displacement reaction with Laser-Induced Breakdown Spectroscopy analysis, referred to as the GDMP-LIBS method. This method can quickly complete the preparation of the micro-particle layer and the displacement reaction of heavy metal elements. By using the developed experimental procedure and optimized experimental parameters, the spectral signals obtained by this method show significant enhancement. For the detection of Cu and Cr, the detection limits are below 1 μg/L, with sensitivity greater than other LIBS methods, and the limits of detection (LoDs) are reduced by several orders of magnitude, even lower than the lowest allowed concentration in relevant authoritative water quality standards by at least one order of magnitude. In the low concentration range from a few μg/L to several tens of μg/L, the quantitative analysis error of this method is small. Overall, as a highly sensitive, rapid, multi-element, and easy-to-operate method for detecting heavy metals in water, the GDMP-LIBS method has the potential for widespread application in the field of heavy metal water quality detection.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107116"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103864","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":"Towards real-time calibration-free LIBS supported by machine learning","authors":"Aurélien Favre ,&nbsp;Alexis Abad ,&nbsp;Alexandre Poux ,&nbsp;Léo Gosse ,&nbsp;Ahmad Berjaoui ,&nbsp;Vincent Morel ,&nbsp;Arnaud Bultel","doi":"10.1016/j.sab.2024.107082","DOIUrl":"10.1016/j.sab.2024.107082","url":null,"abstract":"<div><div>Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) enables multi-elemental quantification without needing standards. This type of approach can be used to analyze complex samples containing traces or gradients of species. This type of diagnosis requires a high level of expertise, and is cumbersome to set up. These constraints limit its application to field diagnostics. Using the MERLIN generalized radiative transfer code, we are able to generate a diversified emission database with no dimensioning limitations. We show that training a convolutional residual network with such a database enables the quantification of 9 species, as well as evaluation of electron density and temperature, without any prior expertise at a rate greater than 10 Hz. The accuracy of this innovative method depends solely on the basic spectroscopic data (emission probabilities and Stark parameters), regardless of the thermodynamic conditions of the laser-induced plasma, as long as it is in Local Thermodynamic Equilibrium (LTE).</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107082"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094309","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":"Precise determination of electrolyte cations in an extracorporeally circulating dialysate with laser-induced breakdown spectroscopy","authors":"Beiyi Zhang ,&nbsp;Qi Zhang ,&nbsp;Zengqi Yue ,&nbsp;Chen Sun ,&nbsp;Feng Ding ,&nbsp;Jin Yu","doi":"10.1016/j.sab.2024.107107","DOIUrl":"10.1016/j.sab.2024.107107","url":null,"abstract":"<div><div>Hemodialysis as the primary renal replacement therapy for patients afflicted by end-stage renal disease, necessitates monitoring of electrolyte cations in the dialysate to ensure the safety and efficacy of the treatment. Concerned elements include calcium, potassium, and sodium. Currently, prevailing detection methods fall short in providing <em>in situ</em> and real-time detection capabilities, highlighting the need of innovation. Elemental analysis of bulk liquids with laser-induced breakdown spectroscopy (LIBS) presents an interesting potential for dialysate monitoring. Methodological research should further aim to achieve simultaneous multi-element determinations in dialysates with high accuracy and precision, using an arrangement compatible with a flowing dialysate and ready for deployment in a clinical environment. In this work, we developed an experimental arrangement tailored for dialysate analysis, integrating an optimized LIBS setup into a circulating dialysate system, which simulated the clinical operation. Such an arrangement allowed generating a stable and hot plasma within a flowing dialysate. The emission lines from calcium, potassium, and sodium were subsequently captured by a detection system optimized for a simultaneous detection of the three elements with concentrations corresponding to those of a real dialysate. Due to self-absorption of the lines, notably self-reversal of the sodium D-lines, univariate regression, usually efficient for processing LIBS spectra of electrolyte cations in a liquid, was revealed insufficient to provide an analytical performance satisfying the requirements of the clinical practice. Data processing based on multivariate regression was thus developed in this work to substantially improve the model prediction performances. More specifically, back-propagation neural networks (BPNN) coupled with feature selection demonstrated the effectiveness to harness the complexity of the spectrum heavily deformed by self-absorption and self-reversal of the characteristic lines. The resulted models exhibit a limit of detection (LOD) of 0.302, 0.571, and 4.25 mmol/L, respectively for Ca, K, and Na. The prediction performances of the trained models were assessed using independent test samples, yielding root mean square errors of prediction (RMSEP) of 0.106, 0.137, and 0.646 mmol/L for Ca, K, and Na, respectively. Such performances satisfy the clinical requirements for monitoring of electrolyte cations in a dialysate.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107107"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094319","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":"XRF data-based statistical clustering of ancient ceramic artifacts and analysing provenance with thermo-mineralogical analysis","authors":"Md Saifur Rahman ,&nbsp;Hendrik Simon Cornelis Metselaar ,&nbsp;Abd Razak Bushroa","doi":"10.1016/j.sab.2024.107090","DOIUrl":"10.1016/j.sab.2024.107090","url":null,"abstract":"<div><div>The chemical composition of a ceramic assemblage 48 sherds from the Museum of Asian Art (MoAA), Universiti Malaya, was determined using X-Ray Fluorescence (XRF) and the statistical analysis of the results was compared with the classification made by the museum curator on the basis of typology. The major objective of this study was to establish a link between the components used to produce Chinese porcelain from Jingdezhen, South China, throughout the different dynasties. A statistical analysis is applied based on 16 major and minor oxides employing hierarchical cluster analysis (HCA), principal component analysis (PCA), biplots, boxplots, and descriptive statistics. Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), and Thermomechanical Analysis (TMA) techniques were used to analyse the material characterization of sherds for classification, resulting in conclusions consistent with provenance and dating. The HCA analysis separated 48 sherds into 5 clusters. Each cluster except cluster 5, lacked of anorthite, which typically forms above temperature 850 °C, indicating that the firing temperature was not exceed 850 °C for clusters 1–4. Similarly, the deformation point for clusters 1–4 were low temperature and high temperature for cluster 5. The observed chemical composition and SiO₂/Al₂O₃ ratio (3.76–4.18) for clusters 1–4 and cluster 5 ratio of 2.92 indicates the Ming and Qing dynasty respectively with origin of Jingdezhen, South China of the examined ceramics. The HCA classification of sherds was based on XRF raw data without combining all experimental techniques like XRD, TMA, and FTIR data. The most representative sherds of each HCA cluster were analyzed thermo-mineralogically. A combination of strong evidence due to material characterization can therefore overcome the hindrance of unreliable sources that cause ambiguity of the sherd's originality and classification.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107090"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103867","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}