Pub Date : 2026-01-01Epub Date: 2025-11-06DOI: 10.1016/j.sab.2025.107385
Bo Wang , Wenbao Jia , Xiaoran Chen , Kai Zeng , Zhichao Zhang , Qing Shan , Yongsheng Ling
The accurate energy-dispersive X-ray fluorescence (EDXRF) analysis of high-silica silicate rocks is notoriously challenging due to their poor cohesiveness, which prevents the formation of stable pressed pellets, and the scarcity of matrix-matched reference materials. To address these limitations, this study introduces a novel integrated methodology that synergistically combines an innovative casting-solidification preparation technique with a robust substitution-dilution quantification algorithm. The preparation method employs metallographic resin to embed powdered samples, effectively overcoming cohesion issues and producing highly homogeneous (RSD < 4 %) and reproducible (RSD < 5.19 %) pellets. The mathematical algorithm leverages a fundamental hyperbolic relationship between the X-ray intensity and the substitution factor, enabling highly accurate quantification of major oxides (SiO2, Al2O3, K2O, CaO) using only a single standard reference material—thereby eliminating the critical dependency on multiple matrix-matched standards. Validation against a range of certified reference materials demonstrated excellent accuracy, with relative errors for major oxides ranging from 1.53 % to 6.72 % . A comprehensive uncertainty evaluation confirmed expanded uncertainties below 7.4 % at a 95 % confidence level. This integrated approach establishes a new, cost-effective, and reliable paradigm for EDXRF analysis of complex silicate materials.
{"title":"Casting-solidification preparation combined with substitution-dilution algorithm for accurate EDXRF analysis of silicate rocks","authors":"Bo Wang , Wenbao Jia , Xiaoran Chen , Kai Zeng , Zhichao Zhang , Qing Shan , Yongsheng Ling","doi":"10.1016/j.sab.2025.107385","DOIUrl":"10.1016/j.sab.2025.107385","url":null,"abstract":"<div><div>The accurate energy-dispersive X-ray fluorescence (EDXRF) analysis of high-silica silicate rocks is notoriously challenging due to their poor cohesiveness, which prevents the formation of stable pressed pellets, and the scarcity of matrix-matched reference materials. To address these limitations, this study introduces a novel integrated methodology that synergistically combines an innovative <!--> <!-->casting-solidification preparation technique with a robust substitution-dilution quantification algorithm. The preparation method employs metallographic resin to embed powdered samples, effectively overcoming cohesion issues and producing highly homogeneous (RSD < 4 %) and reproducible (RSD < 5.19 %) pellets. The mathematical algorithm leverages a fundamental hyperbolic relationship between the X-ray intensity and the substitution factor, enabling highly accurate quantification of major oxides (SiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>, K<sub>2</sub>O, CaO) using only a single standard reference material—thereby eliminating the critical dependency on multiple matrix-matched standards. Validation against a range of certified reference materials demonstrated excellent accuracy, with relative errors for major oxides ranging from 1.53 % to 6.72 %<!--> <!-->. A comprehensive uncertainty evaluation confirmed expanded uncertainties below <!--> <!-->7.4 % at a 95 % confidence level. This integrated approach establishes a new, cost-effective, and reliable paradigm for EDXRF analysis of complex silicate materials.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107385"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517467","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}
Pub Date : 2026-01-01Epub Date: 2025-10-15DOI: 10.1016/j.sab.2025.107360
Zhanjian Lin , Lizhu Kang , Wu Wang , Bing Lu , Xiangyou Li
The detection of elements in liquids is one of the core applications of modern analytical chemistry. Laser-induced breakdown spectroscopy (LIBS) shows significant potential for the detection of elements in liquid samples. The dried droplet method (DDM) avoids liquid splashing, but the coffee-ring effect (CRE) in DDM leads to nonuniform distribution of elements, which can reduce the accuracy of quantitative results. In this work, the exogenous precipitating element addition-controlled uniform precipitation (EPEA-CUP) method was proposed to obtain the uniform distribution of the elements. The mechanism by which the addition of precipitated particles suppressed CRE was analyzed. The distribution of the elements was analyzed macroscopically, while their spectral intensities were examined statistically. Based on the distribution of elements, the internal standard method was applied to correct the matrix effect. The R2 of Ca, Mg and Na were improved from 0.906, 0.933 and 0.802 to 0.949, 0.982 and 0.997, respectively. This method was used to quantitatively detect Mg, Ca, and Na with high precision and accuracy, which provided an efficient idea for the detection of elements in liquid samples.
{"title":"Addition of precipitating element to uniform the distribution of elements in LIBS analysis of liquid samples","authors":"Zhanjian Lin , Lizhu Kang , Wu Wang , Bing Lu , Xiangyou Li","doi":"10.1016/j.sab.2025.107360","DOIUrl":"10.1016/j.sab.2025.107360","url":null,"abstract":"<div><div>The detection of elements in liquids is one of the core applications of modern analytical chemistry. Laser-induced breakdown spectroscopy (LIBS) shows significant potential for the detection of elements in liquid samples. The dried droplet method (DDM) avoids liquid splashing, but the coffee-ring effect (CRE) in DDM leads to nonuniform distribution of elements, which can reduce the accuracy of quantitative results. In this work, the exogenous precipitating element addition-controlled uniform precipitation (EPEA-CUP) method was proposed to obtain the uniform distribution of the elements. The mechanism by which the addition of precipitated particles suppressed CRE was analyzed. The distribution of the elements was analyzed macroscopically, while their spectral intensities were examined statistically. Based on the distribution of elements, the internal standard method was applied to correct the matrix effect. The R<sup>2</sup> of Ca, Mg and Na were improved from 0.906, 0.933 and 0.802 to 0.949, 0.982 and 0.997, respectively. This method was used to quantitatively detect Mg, Ca, and Na with high precision and accuracy, which provided an efficient idea for the detection of elements in liquid samples.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107360"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145364502","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}
Pub Date : 2026-01-01Epub Date: 2025-10-08DOI: 10.1016/j.sab.2025.107356
L. García-Gómez , J.K. Soriano , J.M. Vadillo , Y. Ikeda
The detection of molecular emissions in laser-induced breakdown spectroscopy (LIBS) remains a subject of active research, driven by the need to improve both signal-to-noise ratios and spectral definition. Various enhancement strategies have been proposed, including double-pulse configurations and hybrid systems combining LIBS with complementary techniques like Raman spectroscopy or laser-induced fluorescence. While effective, these methods often introduce considerable experimental complexity. In this context, the present study explores microwave re-excitation (MW-LIBS) as a more accessible alternative capable of modifying plasma dynamics without additional optical alignment. The introduction of microwave energy increases collisional activity within the plasma, extending its duration to the millisecond range and amplifying emission signals. Molecular species were monitored under this regime, focusing on canonical emitters such as CN and CaO, as well as less commonly reported systems like SnO, which has not been previously described in LIBS literature. The most significant enhancements were observed under conditions approaching the plasma ablation threshold. Moreover, MW-LIBS enabled the observation of molecular emissions in the red and near-infrared regions, which are generally limited in conventional LIBS due to detector inefficiencies and reduced plasma radiative output. These findings provide new insights into the mechanisms of molecular formation in sustained plasmas and demonstrate the potential of MW-LIBS for enhancing molecular diagnostics.
{"title":"Improved detection capabilities of molecular emission in microwave-enhanced laser-induced plasma","authors":"L. García-Gómez , J.K. Soriano , J.M. Vadillo , Y. Ikeda","doi":"10.1016/j.sab.2025.107356","DOIUrl":"10.1016/j.sab.2025.107356","url":null,"abstract":"<div><div>The detection of molecular emissions in laser-induced breakdown spectroscopy (LIBS) remains a subject of active research, driven by the need to improve both signal-to-noise ratios and spectral definition. Various enhancement strategies have been proposed, including double-pulse configurations and hybrid systems combining LIBS with complementary techniques like Raman spectroscopy or laser-induced fluorescence. While effective, these methods often introduce considerable experimental complexity. In this context, the present study explores microwave re-excitation (MW-LIBS) as a more accessible alternative capable of modifying plasma dynamics without additional optical alignment. The introduction of microwave energy increases collisional activity within the plasma, extending its duration to the millisecond range and amplifying emission signals. Molecular species were monitored under this regime, focusing on canonical emitters such as CN and CaO, as well as less commonly reported systems like SnO, which has not been previously described in LIBS literature. The most significant enhancements were observed under conditions approaching the plasma ablation threshold. Moreover, MW-LIBS enabled the observation of molecular emissions in the red and near-infrared regions, which are generally limited in conventional LIBS due to detector inefficiencies and reduced plasma radiative output. These findings provide new insights into the mechanisms of molecular formation in sustained plasmas and demonstrate the potential of MW-LIBS for enhancing molecular diagnostics.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107356"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145271003","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}
Pub Date : 2026-01-01Epub Date: 2025-11-13DOI: 10.1016/j.sab.2025.107388
Xingyu Wang, Siyu Liao, Lu Chen, Jiatong Li, Lian Chen, Daqian Hei
Total reflection X-ray fluorescence (TXRF) is a key analytical technique for detecting surface metal contamination on silicon wafers. While mature commercial instruments provide excellent detection performance, they are typically large, heavy, and equipped with high-power X-ray tubes, the use of high-power X-ray tubes (The X-ray tube typically operates at a power of approximately 1500 W.) leads to increased power consumption. In this study, a compact, low-power TXRF-based spectrometer was developed specifically for wafer metal contamination detection. A new quantitative analysis method was employed to mitigate the effects associated with the use of a low-power X-ray tube. The instrument's performance was evaluated using silicon wafers deliberately contaminated with Fe, Ni, and Cu. Elemental mapping and quantitative analysis were conducted using custom Python-based software. The results demonstrate that the spectrometer offers reliable sensitivity and accuracy for detecting surface contaminants on silicon wafers.
{"title":"A compact, low-power total reflection X-ray fluorescence (TXRF) spectrometer designed for surface metal contamination analysis of silicon wafers","authors":"Xingyu Wang, Siyu Liao, Lu Chen, Jiatong Li, Lian Chen, Daqian Hei","doi":"10.1016/j.sab.2025.107388","DOIUrl":"10.1016/j.sab.2025.107388","url":null,"abstract":"<div><div>Total reflection X-ray fluorescence (TXRF) is a key analytical technique for detecting surface metal contamination on silicon wafers. While mature commercial instruments provide excellent detection performance, they are typically large, heavy, and equipped with high-power X-ray tubes, the use of high-power X-ray tubes (The X-ray tube typically operates at a power of approximately 1500 W.) leads to increased power consumption. In this study, a compact, low-power TXRF-based spectrometer was developed specifically for wafer metal contamination detection. A new quantitative analysis method was employed to mitigate the effects associated with the use of a low-power X-ray tube. The instrument's performance was evaluated using silicon wafers deliberately contaminated with Fe, Ni, and Cu. Elemental mapping and quantitative analysis were conducted using custom Python-based software. The results demonstrate that the spectrometer offers reliable sensitivity and accuracy for detecting surface contaminants on silicon wafers.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107388"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517471","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}
This study investigates the mechanisms behind the spectral emission enhancement in Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) compared to conventional Laser-Induced Breakdown Spectroscopy (LIBS). Using a titanium sample coated with 20 nm spherical Au-NPs under optimized conditions, we analyze the temporal evolution of spectral intensity, plasma properties, and ablation characteristics. The results show that NELIBS sustains higher spectral emission for a longer duration while maintaining a relatively lower plasma temperature and higher electron density during plasma expansion. These conditions promote more efficient recombination processes, enhancing continuum emission. Furthermore, spectral analysis reveals that the NELIBS plasma remains optically thin over an extended time window, contributing to improved signal quality. The primary factor driving this enhancement is the increased density of emitting species (ions and atoms), facilitated by improved laser energy absorption, more efficient plasma formation, and modified ablation mechanisms influenced by the localized surface plasmon resonance (LSPR) effect. Furthermore, the microscopic image confirms that NELIBS results in smoother and more uniform ablation craters, indicating superior ablation efficiency. These insights provide deeper insight into the fundamental differences between LIBS and NELIBS, highlighting the advantages of nanoparticle-assisted plasma generation for enhanced spectroscopic performance.
{"title":"Insights into nanoparticle enhanced laser induced breakdown spectroscopy (NELIBS): A comparative study of plasma characteristics and signal enhancement","authors":"Morteza Khalaji, Seyed Hassan Tavassoli, Somayeh Karimi","doi":"10.1016/j.sab.2025.107358","DOIUrl":"10.1016/j.sab.2025.107358","url":null,"abstract":"<div><div>This study investigates the mechanisms behind the spectral emission enhancement in Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) compared to conventional Laser-Induced Breakdown Spectroscopy (LIBS). Using a titanium sample coated with 20 nm spherical Au-NPs under optimized conditions, we analyze the temporal evolution of spectral intensity, plasma properties, and ablation characteristics. The results show that NELIBS sustains higher spectral emission for a longer duration while maintaining a relatively lower plasma temperature and higher electron density during plasma expansion. These conditions promote more efficient recombination processes, enhancing continuum emission. Furthermore, spectral analysis reveals that the NELIBS plasma remains optically thin over an extended time window, contributing to improved signal quality. The primary factor driving this enhancement is the increased density of emitting species (ions and atoms), facilitated by improved laser energy absorption, more efficient plasma formation, and modified ablation mechanisms influenced by the localized surface plasmon resonance (LSPR) effect. Furthermore, the microscopic image confirms that NELIBS results in smoother and more uniform ablation craters, indicating superior ablation efficiency. These insights provide deeper insight into the fundamental differences between LIBS and NELIBS, highlighting the advantages of nanoparticle-assisted plasma generation for enhanced spectroscopic performance.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107358"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145418379","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}
Pub Date : 2026-01-01Epub Date: 2025-11-14DOI: 10.1016/j.sab.2025.107395
Swetapuspa Soumyashree, Prashant Kumar
The present study aims to understand the temporal changes in emission line intensity observed in nanoparticle enhanced LIBS for experiments conducted under different ambient conditions. Although nanoparticles have been extensively used for signal enhancement in LIBS, only a handful of literature exists which discusses their behavior in low-pressure ambient. We have carried out a systematic study of signal enhancement in LIBS in presence of nanoparticles for both neutral and ionic lines in vacuum and air ambient. We have observed 2–3 times signal enhancement in the emission line intensities of neutral species in nanoparticle enhanced LIBS in both ambient. While ionic species show a similar enhancement in air for LIBS with nanoparticles, the trend is opposite in case of vacuum. The observed signal enhancements in LIBS in presence of nanoparticles for both neutral and ionic species were explained through the study of plasma parameters, temperature and electron number density. Temporal evolution of signal enhancements was compared for air and vacuum ambient for both neutral and ionic lines emphasizing the role of acquisition delay and proper selection of emission lines in case of nanoparticle enhanced LIBS.
{"title":"Investigation of signal enhancement of aluminum emission in LIBS using gold nanoparticles in air and vacuum","authors":"Swetapuspa Soumyashree, Prashant Kumar","doi":"10.1016/j.sab.2025.107395","DOIUrl":"10.1016/j.sab.2025.107395","url":null,"abstract":"<div><div>The present study aims to understand the temporal changes in emission line intensity observed in nanoparticle enhanced LIBS for experiments conducted under different ambient conditions. Although nanoparticles have been extensively used for signal enhancement in LIBS, only a handful of literature exists which discusses their behavior in low-pressure ambient. We have carried out a systematic study of signal enhancement in LIBS in presence of nanoparticles for both neutral and ionic lines in vacuum and air ambient. We have observed 2–3 times signal enhancement in the emission line intensities of neutral species in nanoparticle enhanced LIBS in both ambient. While ionic species show a similar enhancement in air for LIBS with nanoparticles, the trend is opposite in case of vacuum. The observed signal enhancements in LIBS in presence of nanoparticles for both neutral and ionic species were explained through the study of plasma parameters, temperature and electron number density. Temporal evolution of signal enhancements was compared for air and vacuum ambient for both neutral and ionic lines emphasizing the role of acquisition delay and proper selection of emission lines in case of nanoparticle enhanced LIBS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107395"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569213","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}
We developed a sample preparation method for total reflection X-ray fluorescence (TXRF) analysis based on a freeze concentration technique to enhance sensitivity. To stabilize the frozen concentration, glycerol, which contains three hydroxyl groups, was added to the sample solution. We also developed a double-internal-reference method for simultaneously determining the concentration rate and the target element concentration before freezing. A Cr-containing sample solution was prepared as the target element, mixed with glycerol and Mn (first internal reference element), and then frozen. The exuded solution was collected and mixed with In (second internal reference element). The concentration rate was determined by comparing the X-ray fluorescence signals of the internal references, whereas the target element concentration was derived from the relationship between the fluorescent X-rays of the target and internal reference elements. Without freeze concentration, the limit of detection (LOD) for Cr using a portable TXRF instrument was 257 ng/mL. With freeze concentration and the addition of glycerol (0.05 mL), the average concentration rate was increased by 29.4-time, improving the LOD to 42.7 ng/mL, and a recovery rate of 100 % was achieved. The freeze concentration combined with a double-internal-reference was proven to be highly effective for sensitive TXRF analysis.
{"title":"Improving limit of detection for Cr in total reflection X-ray fluorescence analysis via freeze concentration with double-internal-reference method","authors":"Tsugufumi Matsuyama , Airi Tsuji , Arinori Inagawa , Lee Wah Lim","doi":"10.1016/j.sab.2025.107390","DOIUrl":"10.1016/j.sab.2025.107390","url":null,"abstract":"<div><div>We developed a sample preparation method for total reflection X-ray fluorescence (TXRF) analysis based on a freeze concentration technique to enhance sensitivity. To stabilize the frozen concentration, glycerol, which contains three hydroxyl groups, was added to the sample solution. We also developed a double-internal-reference method for simultaneously determining the concentration rate and the target element concentration before freezing. A Cr-containing sample solution was prepared as the target element, mixed with glycerol and Mn (first internal reference element), and then frozen. The exuded solution was collected and mixed with In (second internal reference element). The concentration rate was determined by comparing the X-ray fluorescence signals of the internal references, whereas the target element concentration was derived from the relationship between the fluorescent X-rays of the target and internal reference elements. Without freeze concentration, the limit of detection (LOD) for Cr using a portable TXRF instrument was 257 ng/mL. With freeze concentration and the addition of glycerol (0.05 mL), the average concentration rate was increased by 29.4-time, improving the LOD to 42.7 ng/mL, and a recovery rate of 100 % was achieved. The freeze concentration combined with a double-internal-reference was proven to be highly effective for sensitive TXRF analysis.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107390"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569214","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}
Pub Date : 2026-01-01Epub Date: 2025-09-27DOI: 10.1016/j.sab.2025.107342
Pratyush Ranjan Sen Sarma, Maria Teresa Belmonte, Sara Llorente, Santiago Mar
Accurate atomic data for lanthanides, particularly neodymium (Nd), are essential for astrophysical applications, including modelling kilonova opacity and determining stellar abundances. However, reliable experimental data for these ions remain scarce due to the spectral complexity of the lanthanides. In this study, we present a comprehensive characterisation of a high-resolution spectroscopic setup optimised for measuring transition probabilities of Nd lines. The system consists of a 1.5 m Czerny-Turner spectrometer coupled to a high-sensitivity CMOS detector, achieving a resolving power of up to 150,000. A modified hollow cathode lamp, originally developed at Imperial College London, was used to generate a stable neodymium plasma using argon as a carrier gas. We include an in-depth characterisation of our high-resolution setup, including spectral calibration, resolution assessment, instrument response function, and CMOS noise analysis. The validity of the partial local thermodynamic equilibrium (pLTE) assumption in the hollow cathode lamp was tested by measuring transition probabilities for 15 Nd II lines in the spectral range 378–521 nm. The derived transition probabilities show agreement within 30% of the reference values. This validation paves the way for accurate measurements of currently unreported Nd III transition probabilities, providing critical data for future astrophysical modelling efforts.
{"title":"Characterisation of a high-resolution spectroscopic setup for experimental determination of transition probabilities of neodymium","authors":"Pratyush Ranjan Sen Sarma, Maria Teresa Belmonte, Sara Llorente, Santiago Mar","doi":"10.1016/j.sab.2025.107342","DOIUrl":"10.1016/j.sab.2025.107342","url":null,"abstract":"<div><div>Accurate atomic data for lanthanides, particularly neodymium (Nd), are essential for astrophysical applications, including modelling kilonova opacity and determining stellar abundances. However, reliable experimental data for these ions remain scarce due to the spectral complexity of the lanthanides. In this study, we present a comprehensive characterisation of a high-resolution spectroscopic setup optimised for measuring transition probabilities of Nd lines. The system consists of a 1.5 m Czerny-Turner spectrometer coupled to a high-sensitivity CMOS detector, achieving a resolving power of up to 150,000. A modified hollow cathode lamp, originally developed at Imperial College London, was used to generate a stable neodymium plasma using argon as a carrier gas. We include an in-depth characterisation of our high-resolution setup, including spectral calibration, resolution assessment, instrument response function, and CMOS noise analysis. The validity of the partial local thermodynamic equilibrium (pLTE) assumption in the hollow cathode lamp was tested by measuring transition probabilities for 15 Nd II lines in the spectral range 378–521 nm. The derived transition probabilities show agreement within 30% of the reference values. This validation paves the way for accurate measurements of currently unreported Nd III transition probabilities, providing critical data for future astrophysical modelling efforts.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107342"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145364505","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}
Pub Date : 2026-01-01Epub Date: 2025-11-13DOI: 10.1016/j.sab.2025.107391
Shu Hu , Jia Wu , Shangmin Wang , Tao Li , Zihao Liu , Xianglong Cai , Baodong Gai , Ming Xu , Yannan Tan , Jialiang Zhang , Jingwei Guo
The laser-induced ionization of KrHe mixture was used to prepare metastable 5s[3/2]2 level Kr atoms. By analyzing the temporal evolution of the Kr 760.15 nm (5p[3/2]2 → 5s[3/2]2) spectral line intensity, three stages of metastable production were confirmed: the “photon excitation + radiation” process, the “electron-impact excitation + radiation” process, and the “ion-electron recombination” process. In the “electron-impact excitation + radiation” stage, the total collisional decay rate constant for Kr⁎ atoms at the 5p[3/2]2 level associated with the buffer gas He atoms was (0.0179 ± 0.0012) × 10−11 cm3 s−1, which confirmed that under laser-induced ionization, the collision contributions from other levels to the 5p[3/2]2 level Kr atoms were significant. This revealed that He atoms inhibit the reionization of Kr atoms due to their interference and slowing effect on the energy pooling process of Kr atomic levels. In the “ion-electron recombination” stage, the total collisional decay rate constant for Kr⁎ atoms at the 5p[3/2]2 level associated with He atoms was (0.0008 ± 0.0001) × 10−11 cm3 s−1, which was essentially the same as the total collisional decay rate constant for pure Kr gas in this stage. This again indicated that in the continuous recombination process of ions and electrons, the collisional replenishment rate from the Rydberg states to the 5p[3/2]2 level dominates, masking the difference in collisional decay rates between the KrHe mixture and pure Kr gas.
{"title":"Energy transfer mechanism of Kr atoms influenced by He atoms during laser-induced ionization for metastable state generation","authors":"Shu Hu , Jia Wu , Shangmin Wang , Tao Li , Zihao Liu , Xianglong Cai , Baodong Gai , Ming Xu , Yannan Tan , Jialiang Zhang , Jingwei Guo","doi":"10.1016/j.sab.2025.107391","DOIUrl":"10.1016/j.sab.2025.107391","url":null,"abstract":"<div><div>The laser-induced ionization of Kr<img>He mixture was used to prepare metastable 5s[3/2]<sub>2</sub> level Kr atoms. By analyzing the temporal evolution of the Kr 760.15 nm (5p[3/2]<sub>2</sub> → 5s[3/2]<sub>2</sub>) spectral line intensity, three stages of metastable production were confirmed: the “photon excitation + radiation” process, the “electron-impact excitation + radiation” process, and the “ion-electron recombination” process. In the “electron-impact excitation + radiation” stage, the total collisional decay rate constant for Kr<sup>⁎</sup> atoms at the 5p[3/2]<sub>2</sub> level associated with the buffer gas He atoms was (0.0179 ± 0.0012) × 10<sup>−11</sup> cm<sup>3</sup> s<sup>−1</sup>, which confirmed that under laser-induced ionization, the collision contributions from other levels to the 5p[3/2]<sub>2</sub> level Kr atoms were significant. This revealed that He atoms inhibit the reionization of Kr atoms due to their interference and slowing effect on the energy pooling process of Kr atomic levels. In the “ion-electron recombination” stage, the total collisional decay rate constant for Kr<sup>⁎</sup> atoms at the 5p[3/2]<sub>2</sub> level associated with He atoms was (0.0008 ± 0.0001) × 10<sup>−11</sup> cm<sup>3</sup> s<sup>−1</sup>, which was essentially the same as the total collisional decay rate constant for pure Kr gas in this stage. This again indicated that in the continuous recombination process of ions and electrons, the collisional replenishment rate from the Rydberg states to the 5p[3/2]<sub>2</sub> level dominates, masking the difference in collisional decay rates between the Kr<img>He mixture and pure Kr gas.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107391"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517470","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}
Pub Date : 2026-01-01Epub Date: 2025-11-10DOI: 10.1016/j.sab.2025.107383
Tianyang Sun, Yunfei Rao, Li Wang, Ding Li, Haoyu Yang, Chen Sun, Jin Yu
Determination of nitrogen in solid-state materials using laser-induced breakdown spectroscopy (LIBS) under the atmospheric pressure faces the challenge of interference from nitrogen present in the ambient gas. Previous studies have proposed various strategies to address this issue, such as employing a vacuum chamber or purging the laser interaction zone with an inert gas, with the cost of increasing the complexity of a LIBS instrument. Fiber lasers with their recent industrial development present a promising opportunity for LIBS applications due to their inherent advantages, such as compactness, stability, and cost-effectiveness. Determination of a nonmetal element such as nitrogen in solid-state materials using a fiber laser remains to be demonstrated. Performing a such demonstration, with a particular focus on investigating an interference-free regime in LIBS operation, is precisely the purpose of this work. A series of nitrogen-bearing samples was prepared using cement as the matrix material and silicon nitride as the nitrogen-containing dopant. The experiments were conducted using a commercially available Q-switched Nd:YAG fiber laser operating at 1064 nm, with a pulse duration of 100 ns, a repetition rate of 5 kHz, and a pulse energy of 640 μJ. The N I 744.2 nm emission line was clearly observed, and our investigation confirmed that it originated from the sample rather than the ambient gas. This enabled a univariate regression of the spectral intensity against the nitrogen concentration. To further improve the analytical performance, feature selection was combined with multivariate regression using the partial least squares (PLS) algorithm. The resulting model achieved a limit of detection (LOD) of 0.46 wt%, a relative error of prediction (REP) of 2.22 %, and a root mean square error of prediction (RMSEP) of 0.12 wt%. Such results represent a significant improvement with respect to the state-of-art performance for nitrogen determination in solid-state materials with LIBS, with for example a reported LOD of 0.8 wt% for a determination of nitrogen in sands (Harris et al., 2004 [1]), demonstrating thus the capability of fiber laser LIBS for accurate nitrogen determination in solid-state materials under the atmospheric conditions, without the need of additional equipment such as vacuum or gas purging systems.
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