Pub Date : 2025-12-11DOI: 10.1016/j.sab.2025.107425
Victor M. Chubarov , Alexandr L. Finkelshtein , Galina V. Pashkova , Tatyana A. Radomskaya
An approach utilizing the intensity ratio of copper L-series X-ray emission lines was developed to determine copper mineral forms. Minerals containing predominantly monovalent copper as sulfides (chalcocite, bornite) and oxides (cuprite), as well as divalent copper as sulfides (chalcopyrite) and sulfates (antlerite, brochantite) were studied. A conventional wavelength-dispersive X-ray fluorescence spectrometer with moderate energy resolution (around 15–20 eV at the CuLα line energy (930 eV)) was used for measurements. This resolution is not sufficient to completely resolve the CuLβ and CuLα lines. However, the ratio of the CuLβ and CuLα line intensities differed significantly among various copper minerals: from 0.23 to 0.24 for cuprite and chalcocite to 0.43–0.44 for malachite, antlerite, and brochantite. Investigation of copper‑nickel ores enabled the identification of chalcopyrite as the main copper-containing mineral, which corresponds to X-ray powder diffraction data.
{"title":"WDXRF technique for the assessment of copper valence state and mineral form using L-series lines","authors":"Victor M. Chubarov , Alexandr L. Finkelshtein , Galina V. Pashkova , Tatyana A. Radomskaya","doi":"10.1016/j.sab.2025.107425","DOIUrl":"10.1016/j.sab.2025.107425","url":null,"abstract":"<div><div>An approach utilizing the intensity ratio of copper L-series X-ray emission lines was developed to determine copper mineral forms. Minerals containing predominantly monovalent copper as sulfides (chalcocite, bornite) and oxides (cuprite), as well as divalent copper as sulfides (chalcopyrite) and sulfates (antlerite, brochantite) were studied. A conventional wavelength-dispersive X-ray fluorescence spectrometer with moderate energy resolution (around 15–20 eV at the CuLα line energy (930 eV)) was used for measurements. This resolution is not sufficient to completely resolve the CuLβ and CuLα lines. However, the ratio of the CuLβ and CuLα line intensities differed significantly among various copper minerals: from 0.23 to 0.24 for cuprite and chalcocite to 0.43–0.44 for malachite, antlerite, and brochantite. Investigation of copper‑nickel ores enabled the identification of chalcopyrite as the main copper-containing mineral, which corresponds to X-ray powder diffraction data.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107425"},"PeriodicalIF":3.8,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737948","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 : 2025-12-06DOI: 10.1016/j.sab.2025.107421
Yuqi Hu , Dan Yu , Yuanfei Jiang , Anmin Chen , Mingxing Jin
Nanoparticle-enhanced laser-induced breakdown spectroscopy (NELIBS) has attracted significant attention due to its ability to enhance spectral signals and detection sensitivity. However, previous studies have mainly employed nanosecond lasers as excitation sources, and systematic investigations into the enhancement mechanism and concentration optimization under femtosecond laser conditions remain limited. This experiment employed a femtosecond laser with a wavelength of 800 nm and a pulse width of 35 fs. Gold nanoparticle dispersions with varying concentrations (0–125 μg/mL) were dropped onto the surfaces of brass and aluminum substrates, followed by LIBS analysis after drying. The results showed that the spectral intensity and signal-to-noise ratio (SNR) of Cu(I) at 510.5 nm and Al(I) at 396.1 nm increased initially and then decreased as the gold nanoparticle concentration increased. Within the optimal concentration range (3.9–31.25 μg/mL), the intensities of the Cu(I) and Al(I) lines increased by up to approximately 2.3-fold and 1.6-fold, respectively, while the SNR improved by about 2-fold, compared to those without gold nanoparticles (Au NPs). Within this range, the relative standard deviation (RSD) of the spectral intensity was below approximately 20 %; beyond this range, the RSD increased significantly, indicating reduced signal stability. The variation trend of the apparent plasma temperature with concentration was consistent with that of spectral intensity, while the apparent electron density showed a decreasing trend. This study provides an experimental basis for the optimization of NELIBS under femtosecond laser excitation.
{"title":"Concentration effects of gold nanoparticles on spectral enhancement and plasma parameters in femtosecond LIBS","authors":"Yuqi Hu , Dan Yu , Yuanfei Jiang , Anmin Chen , Mingxing Jin","doi":"10.1016/j.sab.2025.107421","DOIUrl":"10.1016/j.sab.2025.107421","url":null,"abstract":"<div><div>Nanoparticle-enhanced laser-induced breakdown spectroscopy (NELIBS) has attracted significant attention due to its ability to enhance spectral signals and detection sensitivity. However, previous studies have mainly employed nanosecond lasers as excitation sources, and systematic investigations into the enhancement mechanism and concentration optimization under femtosecond laser conditions remain limited. This experiment employed a femtosecond laser with a wavelength of 800 nm and a pulse width of 35 fs. Gold nanoparticle dispersions with varying concentrations (0–125 μg/mL) were dropped onto the surfaces of brass and aluminum substrates, followed by LIBS analysis after drying. The results showed that the spectral intensity and signal-to-noise ratio (SNR) of Cu(I) at 510.5 nm and Al(I) at 396.1 nm increased initially and then decreased as the gold nanoparticle concentration increased. Within the optimal concentration range (3.9–31.25 μg/mL), the intensities of the Cu(I) and Al(I) lines increased by up to approximately 2.3-fold and 1.6-fold, respectively, while the SNR improved by about 2-fold, compared to those without gold nanoparticles (Au NPs). Within this range, the relative standard deviation (RSD) of the spectral intensity was below approximately 20 %; beyond this range, the RSD increased significantly, indicating reduced signal stability. The variation trend of the apparent plasma temperature with concentration was consistent with that of spectral intensity, while the apparent electron density showed a decreasing trend. This study provides an experimental basis for the optimization of NELIBS under femtosecond laser excitation.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107421"},"PeriodicalIF":3.8,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737851","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}
Monitoring trace metal elements in lubricating oils of aero-engines is crucial for evaluating wear conditions and predicting service life. In this work, a self-absorption-autocompensated discharge-assisted LIBS (SAAC-DA-LIBS) technique is proposed for trace element analysis in lubricating oils. The transient discharge field in DA-LIBS was modulated by optimizing spark discharge and arc discharge, thereby enhancing the plasma spectral intensity by two orders of magnitude. The SAAC, based on self-autocalibration of doublet lines, evaluates the self-absorption effect, and further infers the ideal spectral intensity. Accordingly, the linearity of the calibration curve is significantly improved over a wide concentration range. The limits of detection (LODs) for the typical elements, Ca, Ba, and Na, are substantially reduced from 94.21 μmol/mol, 33.31 μmol/mol, and 50.75 μmol/mol in SP-LIBS to 0.91 μmol/mol, 0.31 μmol/mol, and 1.50 μmol/mol in SAAC-DA-LIBS, respectively, exhibiting a sensitivity improvement by more than two orders of magnitude. Moreover, the recovery rate approaches 100 %, guaranteeing a superior recovery performance of SAAC-DA-LIBS. Thus, SAAC-DA-LIBS emerges as an ultrasensitive and high-accuracy technique with strong potential for in situ, real-time detection of lubricants, offering a promising approach to enhancing aviation safety.
{"title":"Ultrasensitive and high-accuracy trace detection by using self-absorption-autocompensated discharge-assisted LIBS for reinforcing aircraft safety","authors":"Boping Xu , Peiqi Yin , Jiajia Hou , Xukun Yin , Jie Tang , Dacheng Zhang , Huailiang Xu","doi":"10.1016/j.sab.2025.107416","DOIUrl":"10.1016/j.sab.2025.107416","url":null,"abstract":"<div><div>Monitoring trace metal elements in lubricating oils of aero-engines is crucial for evaluating wear conditions and predicting service life. In this work, a self-absorption-autocompensated discharge-assisted LIBS (SAAC-DA-LIBS) technique is proposed for trace element analysis in lubricating oils. The transient discharge field in DA-LIBS was modulated by optimizing spark discharge and arc discharge, thereby enhancing the plasma spectral intensity by two orders of magnitude. The SAAC, based on self-autocalibration of doublet lines, evaluates the self-absorption effect, and further infers the ideal spectral intensity. Accordingly, the linearity of the calibration curve is significantly improved over a wide concentration range. The limits of detection (LODs) for the typical elements, Ca, Ba, and Na, are substantially reduced from 94.21 μmol/mol, 33.31 μmol/mol, and 50.75 μmol/mol in SP-LIBS to 0.91 μmol/mol, 0.31 μmol/mol, and 1.50 μmol/mol in SAAC-DA-LIBS, respectively, exhibiting a sensitivity improvement by more than two orders of magnitude. Moreover, the recovery rate approaches 100 %, guaranteeing a superior recovery performance of SAAC-DA-LIBS. Thus, SAAC-DA-LIBS emerges as an ultrasensitive and high-accuracy technique with strong potential for in situ, real-time detection of lubricants, offering a promising approach to enhancing aviation safety.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107416"},"PeriodicalIF":3.8,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737947","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 : 2025-12-04DOI: 10.1016/j.sab.2025.107404
Alena A. Amosova, Victor M. Chubarov, Julia V. Sokolnikova, Sergey N. Prosekin, Alexandr L. Finkelshtein
X-ray fluorescence analysis of snow cover solid phase samples collected near aluminum smelter facilities is a promising method for investigating environmental pollution. Key issues in determining fluorine by X-ray fluorescence method in these samples are the lack of matrix-matched reference materials and the strong dependence of the FKα line intensity on fluorine's chemical state. To address this, we considered artificial mixtures for calibration, prepared from soil reference materials, alumina, and various fluorine compounds (such as fluorite, synthetic cryolite, and aluminum fluoride), along with reference materials of apatite ores and granites. Measurements were performed using a wavelength-dispersive spectrometer. The selection of optimal measurement conditions minimized the influence of spectral overlaps and other factors affecting the FKα line intensity. Artificial mixtures based on both aluminum fluoride and synthetic cryolite were chosen as optimal calibration set. For snow cover solid phase samples collected near the Irkutsk Aluminum Smelter (Irkutsk district, Russia), a comparison of the proposed X-ray fluorescence analysis method with potentiometry showed a root mean square deviation of 0.15 wt% for fluorine content range from 0.4 to 1.6 wt%. Furthermore, comparing the data from these two techniques allows for inferences regarding the probable chemical forms of fluorine present in analyzed samples.
{"title":"X-ray fluorescence determination of fluorine in snow cover solid phase for investigation of aluminum industry emissions","authors":"Alena A. Amosova, Victor M. Chubarov, Julia V. Sokolnikova, Sergey N. Prosekin, Alexandr L. Finkelshtein","doi":"10.1016/j.sab.2025.107404","DOIUrl":"10.1016/j.sab.2025.107404","url":null,"abstract":"<div><div>X-ray fluorescence analysis of snow cover solid phase samples collected near aluminum smelter facilities is a promising method for investigating environmental pollution. Key issues in determining fluorine by X-ray fluorescence method in these samples are the lack of matrix-matched reference materials and the strong dependence of the FKα line intensity on fluorine's chemical state. To address this, we considered artificial mixtures for calibration, prepared from soil reference materials, alumina, and various fluorine compounds (such as fluorite, synthetic cryolite, and aluminum fluoride), along with reference materials of apatite ores and granites. Measurements were performed using a wavelength-dispersive spectrometer. The selection of optimal measurement conditions minimized the influence of spectral overlaps and other factors affecting the FKα line intensity. Artificial mixtures based on both aluminum fluoride and synthetic cryolite were chosen as optimal calibration set. For snow cover solid phase samples collected near the Irkutsk Aluminum Smelter (Irkutsk district, Russia), a comparison of the proposed X-ray fluorescence analysis method with potentiometry showed a root mean square deviation of 0.15 wt% for fluorine content range from 0.4 to 1.6 wt%. Furthermore, comparing the data from these two techniques allows for inferences regarding the probable chemical forms of fluorine present in analyzed samples.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107404"},"PeriodicalIF":3.8,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683118","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 : 2025-12-03DOI: 10.1016/j.sab.2025.107420
Daniel Diaz , Amir Fayyaz , Muhammad Aslam Baig , Tyler Wilson , David W. Hahn
Laser-induced breakdown spectroscopy (LIBS) was used to characterize non-matrix matched certified reference materials containing the rare earth elements La, Nd, Pr, and the actinide metal Th. LIBS characterization included the creation of calibration curves, calculation of limits of detection and quantification, sample classification by matrix type, and evaluation of the sample homogeneity using LIBS chemical maps. Eleven commercial certified reference materials from four different matrices were prepared as pressed pellets and analyzed with LIBS. A single univariate calibration curve for each analyte that included samples from all four matrices was obtained, demonstrating the possibility of non-matrix matched chemical analysis and the strong dependence of LIBS performance with the pellet quality. The limits of detection and quantification were below the nominal earth's crustal abundance of the analytes. Sample clustering and classification by matrix type was possible by applying principal component analysis to the combined spectral data from six 26-nm-width spectral windows. Finally, 2D LIBS chemical mapping was carried out to assess the spatial surface distribution of the analytes on the pellets.
{"title":"Laser-induced breakdown spectroscopy for the characterization of certified reference materials containing rare earth elements","authors":"Daniel Diaz , Amir Fayyaz , Muhammad Aslam Baig , Tyler Wilson , David W. Hahn","doi":"10.1016/j.sab.2025.107420","DOIUrl":"10.1016/j.sab.2025.107420","url":null,"abstract":"<div><div>Laser-induced breakdown spectroscopy (LIBS) was used to characterize non-matrix matched certified reference materials containing the rare earth elements La, Nd, Pr, and the actinide metal Th. LIBS characterization included the creation of calibration curves, calculation of limits of detection and quantification, sample classification by matrix type, and evaluation of the sample homogeneity using LIBS chemical maps. Eleven commercial certified reference materials from four different matrices were prepared as pressed pellets and analyzed with LIBS. A single univariate calibration curve for each analyte that included samples from all four matrices was obtained, demonstrating the possibility of non-matrix matched chemical analysis and the strong dependence of LIBS performance with the pellet quality. The limits of detection and quantification were below the nominal earth's crustal abundance of the analytes. Sample clustering and classification by matrix type was possible by applying principal component analysis to the combined spectral data from six 26-nm-width spectral windows. Finally, 2D LIBS chemical mapping was carried out to assess the spatial surface distribution of the analytes on the pellets.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107420"},"PeriodicalIF":3.8,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737946","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 : 2025-12-02DOI: 10.1016/S0584-8547(25)00290-3
{"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)00290-3","DOIUrl":"10.1016/S0584-8547(25)00290-3","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107405"},"PeriodicalIF":3.8,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681286","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 : 2025-12-02DOI: 10.1016/j.sab.2025.107419
Xing Han , Zhenxiao Li , Haibin Tang
The spectroscopic measurement method for determination of tungsten density is presented by plasma diagnostics and theoretical modeling of spectra. The collision-radiation model applicable to small amounts of tungsten in a high-density plasma is constructed to calculate the densities of neutral tungsten, singly ionized tungsten, and doubly ionized tungsten. The processes taken into account are radiative decay, electron impact excitation, electron impact deexcitation, electron impact ionization, and three-body recombination processes. The densities of different ionization states of tungsten for an applied-field magnetoplasmadynamic thruster cathode at different working currents and magnetic field intensities are diagnosed for verifying the method’s applicability. The experimental results and metallographic analysis of the material show that the lattice structure of the tungsten cathode surface has recrystallized after long-term plasma interaction, resulting in enlarged grain sizes and consequently enhanced erosion resistance.
{"title":"Tungsten collision-radiation model development and density measurement in argon plasma arc","authors":"Xing Han , Zhenxiao Li , Haibin Tang","doi":"10.1016/j.sab.2025.107419","DOIUrl":"10.1016/j.sab.2025.107419","url":null,"abstract":"<div><div>The spectroscopic measurement method for determination of tungsten density is presented by plasma diagnostics and theoretical modeling of spectra. The collision-radiation model applicable to small amounts of tungsten in a high-density plasma is constructed to calculate the densities of neutral tungsten, singly ionized tungsten, and doubly ionized tungsten. The processes taken into account are radiative decay, electron impact excitation, electron impact deexcitation, electron impact ionization, and three-body recombination processes. The densities of different ionization states of tungsten for an applied-field magnetoplasmadynamic thruster cathode at different working currents and magnetic field intensities are diagnosed for verifying the method’s applicability. The experimental results and metallographic analysis of the material show that the lattice structure of the tungsten cathode surface has recrystallized after long-term plasma interaction, resulting in enlarged grain sizes and consequently enhanced erosion resistance.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107419"},"PeriodicalIF":3.8,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145737849","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 : 2025-12-02DOI: 10.1016/j.sab.2025.107418
Peng Wang , Tao He , Jianyu Wang , Jiufen Liu , Feirong Meng , Qianni Men , Liming Gan , Xiaowen Jin , Boxin Feng
Activated carbon enrichment combined with flame atomic absorption spectrometry (FAAS) offers a robust approach for gold analysis in geological samples, featuring a wide determination range (e.g., 0.32–92 g t−1 in this study), good reproducibility, and high accuracy. However, its performance is influenced by multiple factors—activated carbon consumption, ash content, adsorption column layers, and washing temperature—requiring systematic optimization. This study addresses this challenge by applying an integrated model that combines the EW theory and technique for order preference by similarity to ideal solution (TOPSIS). Single-factor experiments were first conducted to determine the operational ranges for these four key parameters. A mixed orthogonal design was then implemented, using the absolute relative error (RE) at three gold concentrations (51.8, 18.3, 1.1 μg g−1) as the evaluation index. The EW method objectively assigned weights (0.3120, 0.3219, 0.3661) to these levels, and TOPSIS calculated relative closeness coefficients to rank all experiments. Range analysis identified the optimal parameter combination. Validation under optimized conditions using certified reference materials (GBW(E)070012a, GBW07808b, GBW07809a, GBW07810) confirmed high reliability, with RE and RSD values of 0.11 %–4.69 % and 0.43 %–8.35 %, respectively, complying with industry standard DZ/T 0130.3–2006. The principal novelty of this work lies in the first objective, data-driven application of the integrated EW-TOPSIS model to multi-parameter optimization in FAAS-based geochemical analysis, establishing a transferable paradigm that enhances methodological robustness and operational efficiency in analytical laboratories.
活性炭富集结合火焰原子吸收光谱法（FAAS）为地质样品中的金分析提供了一种可靠的方法，具有测定范围宽（例如，本研究的测定范围为0.32-92 g t - 1），重复性好，准确性高的特点。但其性能受活性炭用量、灰分、吸附柱层数、洗涤温度等因素的影响，需要系统优化。本研究通过应用集成模型解决了这一挑战，该模型结合了电子战理论和理想解相似性排序偏好技术（TOPSIS）。首先进行单因素实验，确定这四个关键参数的作用范围。以3种金浓度（51.8、18.3、1.1 μg−1）下的绝对相对误差（RE）为评价指标，进行混合正交设计。EW方法客观地为这些水平分配权重（0.3120,0.3219,0.3661），TOPSIS计算相对接近系数对所有实验进行排序。极差分析确定了最佳的参数组合。采用标准物质（GBW(E)070012a、GBW07808b、GBW07809a、GBW07810）在优化条件下进行验证，可靠性高，RE和RSD值分别为0.11% ~ 4.69%和0.43% ~ 8.35%，符合行业标准DZ/T 0130.3-2006。这项工作的主要新颖之处在于第一个客观的、数据驱动的综合EW-TOPSIS模型应用于基于faas的地球化学分析的多参数优化，建立了一个可转移的范例，提高了分析实验室的方法稳健性和操作效率。
{"title":"Application of the integrated entropy weight and Technique for Order of Preference by Similarity to Ideal Solution model in optimizing the sample pretreatment process for gold analysis in gold ore by Flame Atomic Absorption Spectrometry","authors":"Peng Wang , Tao He , Jianyu Wang , Jiufen Liu , Feirong Meng , Qianni Men , Liming Gan , Xiaowen Jin , Boxin Feng","doi":"10.1016/j.sab.2025.107418","DOIUrl":"10.1016/j.sab.2025.107418","url":null,"abstract":"<div><div>Activated carbon enrichment combined with flame atomic absorption spectrometry (FAAS) offers a robust approach for gold analysis in geological samples, featuring a wide determination range (e.g., 0.32–92 g t<sup>−1</sup> in this study), good reproducibility, and high accuracy. However, its performance is influenced by multiple factors—activated carbon consumption, ash content, adsorption column layers, and washing temperature—requiring systematic optimization. This study addresses this challenge by applying an integrated model that combines the EW theory and technique for order preference by similarity to ideal solution (TOPSIS). Single-factor experiments were first conducted to determine the operational ranges for these four key parameters. A mixed orthogonal design was then implemented, using the absolute relative error (RE) at three gold concentrations (51.8, 18.3, 1.1 μg g<sup>−1</sup>) as the evaluation index. The EW method objectively assigned weights (0.3120, 0.3219, 0.3661) to these levels, and TOPSIS calculated relative closeness coefficients to rank all experiments. Range analysis identified the optimal parameter combination. Validation under optimized conditions using certified reference materials (GBW(E)070012a, GBW07808b, GBW07809a, GBW07810) confirmed high reliability, with RE and RSD values of 0.11 %–4.69 % and 0.43 %–8.35 %, respectively, complying with industry standard DZ/T 0130.3–2006. The principal novelty of this work lies in the first objective, data-driven application of the integrated EW-TOPSIS model to multi-parameter optimization in FAAS-based geochemical analysis, establishing a transferable paradigm that enhances methodological robustness and operational efficiency in analytical laboratories.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107418"},"PeriodicalIF":3.8,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683058","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 : 2025-12-01DOI: 10.1016/j.sab.2025.107417
Wei Zhao, Xianyun Ai, Wenhui Li
Energy resolution and matrix effects hinder the widespread application of energy-dispersive X-ray fluorescence spectroscopy in analyzing unknown samples. To address these limitations, this paper proposes a novel automatic and standardless elemental analysis method. This method integrates deconvolution with fundamental parameters model in a closed iterative framework: deconvolution first enhances spectral resolution to improve qualitative element identification, and the fundamental parameters model then quantifies elemental contents with qualitative results dynamically feeding back to input to the fundamental parameters model, forming a tightly coupled qualitative-quantitative loop. The approach was validated using multi-element certified reference materials and the results were compared with those obtained from the commercial software XRS-FP2. The findings confirm that the proposed method enables automated end-to-end elemental analysis without reference materials, and contributes to mitigating the bottlenecks of peak overlap and matrix effects in unknown sample analysis. It thus provides a practical analytical tool for rapid and reliable elemental analysis.
{"title":"An automated, standardless method for elemental analysis in EDXRF based on spectral deconvolution for resolution enhancement","authors":"Wei Zhao, Xianyun Ai, Wenhui Li","doi":"10.1016/j.sab.2025.107417","DOIUrl":"10.1016/j.sab.2025.107417","url":null,"abstract":"<div><div>Energy resolution and matrix effects hinder the widespread application of energy-dispersive X-ray fluorescence spectroscopy in analyzing unknown samples. To address these limitations, this paper proposes a novel automatic and standardless elemental analysis method. This method integrates deconvolution with fundamental parameters model in a closed iterative framework: deconvolution first enhances spectral resolution to improve qualitative element identification, and the fundamental parameters model then quantifies elemental contents with qualitative results dynamically feeding back to input to the fundamental parameters model, forming a tightly coupled qualitative-quantitative loop. The approach was validated using multi-element certified reference materials and the results were compared with those obtained from the commercial software XRS-FP2. The findings confirm that the proposed method enables automated end-to-end elemental analysis without reference materials, and contributes to mitigating the bottlenecks of peak overlap and matrix effects in unknown sample analysis. It thus provides a practical analytical tool for rapid and reliable elemental analysis.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107417"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683116","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 : 2025-11-29DOI: 10.1016/j.sab.2025.107402
Lu Wang , Xi-Ming Zhu , Tian-Yuan Ji , Yang Wang , Klaus Bartschat , Qiu-Yao Cao , Li-Qiu Wei
Metal plasma has been widely applied in hard coatings or metallization of vias and trenches in semiconductor device fabrication. Ion irradiation plays a vital role in the film properties. Previous methods have focused on the Ti atom and Ti+ ion number densities; however, there is a lack of a practical optical emission spectroscopy method for measuring the Ti2+ ion number density. High-charge-state ions lead to high compressive stress, especially in high-power impulse magnetron sputtering (HiPIMS) and vacuum arc plasma devices with a high ionization fraction. In this work, we present a novel charge-state resolved OES method to obtain the time-resolved Ti+ and Ti2+ ion number densities. This method is based on the excited-state cycle mechanisms of Ti+(4p) and Ti2+(4p) emitting states, as determined by kinetic investigations using a collisional-radiative model. In the excited-state cycle mechanisms, the Ti+/Ti2+ line-ratio is found to be sensitive to the ion ratio, and the Ti2+ line-ratio is sensitive to the electron density. The latter can decouple the influence of the electron density on the Ti+/Ti2+ line ratio, allowing the Ti+ and Ti2+ ion number densities to be determined by combining the above line ratios. This method is verified in a vacuum arc titanium metal plasma source.
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