Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

{"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":"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":"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":"Relativistic and semi-theoretical calculations of K-shell to L-shell/subshell vacancy transfer probabilities","authors":"Boualem Berkani ,&nbsp;Abdelhalim Kahoul ,&nbsp;Jorge Miguel Sampaio ,&nbsp;Salim Daoudi ,&nbsp;José Pires Marques ,&nbsp;Fernando Parente ,&nbsp;Assala Hamidani ,&nbsp;Stephen Croft ,&nbsp;Andrea Favalli ,&nbsp;Yazid Kasri ,&nbsp;Amina Zidi ,&nbsp;Kahina Amari","doi":"10.1016/j.sab.2024.107089","DOIUrl":"10.1016/j.sab.2024.107089","url":null,"abstract":"<div><div>In this study, we use the relativistic multiconfiguration Dirac–Fock method (MCFD) to compute the probabilities of radiative and radiationless vacancy transfer from K- to L₁-, L₂-, and L₃₋ subshells in ₁₆S, ₁₈Ar, ₂₂Ti, ₂₉Cu, ₃₀Zn, ₃₂Ge, ₃₃As, ₃₄Se, ₃₆Kr, ₄₀Zr, ₄₈Cd, ₅₀Sn, ₅₂Te, ₈₀Hg, ₈₃Bi, and ₈₆Rn atoms. Semi-theoretical calculations for elements within the atomic range of 18 ≤ <em>Z</em> ≤ 96 (₁₈Ar to ₉₆Cm) were also conducted, leveraging available data on radiative and radiationless transitions from the scientific literature. The theoretical calculation results aligned well with the values calculated semi-theoretically and with other published works. However, some notable differences were identified.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107089"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094307","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}

{"title":"Study on ablation behavior and mechanism for accurate determination of rare earth elements in CaF2 crystals by UV-LA-ICP-MS","authors":"Yuqiu Ke ,&nbsp;Hui Hu ,&nbsp;Jianzong Zhou ,&nbsp;Haitao Li ,&nbsp;Yu Zhang ,&nbsp;Chaoyang Tu ,&nbsp;Herui Wen ,&nbsp;Yijian Sun","doi":"10.1016/j.sab.2024.107091","DOIUrl":"10.1016/j.sab.2024.107091","url":null,"abstract":"<div><div>Catastrophic ablation of CaF₂ crystals is often observed in ultraviolet-laser ablation-inductively coupled plasma-mass spectrometry (UV-LA-ICP-MS) analysis, leading to variations in the volume of ablated material and resulting analytical errors in LA-ICP-MS microanalysis. Therefore, it is essential to understand the ablation behavior and the interaction mechanisms between the laser and CaF₂ crystals. In this study, we examined the effects of crystal surface roughness and laser fluence on ablation behavior. The CaF₂ crystal polished with 1500 mesh abrasive paper exhibited a stable signal profile, a regular ablation crater, and the formation of nanoparticles, which align with predictions from the thermo-mechanical coupling model. Both higher and lower roughness resulted in either unstable ablation or uncontrolled ejection of fragments; the latter occurred when the thermal stress from accumulated light energy significantly exceeded the compressive strength of CaF₂. Consequently, a roughness of 1500 mesh at the bottom of the ablation craters was deduced. We also identified a laser fluence of 14 J·cm⁻² as the threshold for effective LA-ICP-MS analysis of CaF₂ crystals, based on consistent signal profiles, elemental fractionation index (EFI), and crater morphology as revealed by LA-ICP-MS and scanning electron microscope (SEM) analyses, along with theoretical calculations from the thermo-mechanical coupling model. The optimal roughness (1500 mesh) and fluence (14 J·cm⁻²), together with the thermo-mechanical coupling model, can serve as guidelines for UV-LA-ICP-MS settings in further quantitative analyses of CaF₂ crystals.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107091"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094308","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":"Surface and in-depth characterization of commercial papers by LIBS technique: Parameters and features for their classification, and complementary information from Raman spectroscopy","authors":"Flavio Cicconi ,&nbsp;Violeta Lazic","doi":"10.1016/j.sab.2024.107112","DOIUrl":"10.1016/j.sab.2024.107112","url":null,"abstract":"<div><div>In examination of documents by LIBS technique, the paper material is usually probed by surface scanning and the averaged spectra are processed by chemometric methods. The scope of this work is to have insight into LIBS analysis of common writing/printing papers, considering both the laser depth profiling and surface measurements. The sample set consisted in 14 papers (copy, notebook and envelope papers), some of them made of recycled materials. Examination of the laser induced craters showed a preferential ablation of paper fillers while the cellulose fibres were displaced at surface and swallowed around the centre of laser spot. Beside material inclusions, found both on the paper surface and in depth, the not uniform ablation also contributes to large intensity fluctuations of the element's line intensities, which standard deviations differ from one sample to another. By studying correlations between the line intensities from different elements at paper surface and in depth, it was possible to distinguish some top coatings (e.g., kaolinite) from bulk fillers (e.g., containing alumina-silicates), to hypothesize the use of NaOH in the industrial processing, as well as to exclude presence of certain types of fillers or coatings. Raman spectroscopy was performed both on sample surfaces and inside the laser induced craters (bulk material), showing the differences among papers regarding relative contents of CaCO₃ filler, lignin, and cellulose. We tested different chemometric models based on the LIBS measured composition of paper bulk or surface, obtaining up to 100 % correct classification for six similar copy papers of Italian manufacture.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107112"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103860","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}