Accurate monitoring of serum potassium (K) levels is essential for clinical diagnostics due to their vital roles in maintaining physiological functions. Although laser-induced breakdown spectroscopy (LIBS) enables rapid elemental analysis, its limited sensitivity and precision restrict its effectiveness in quantifying K in complex biological samples. This study explores the application of silver nanoparticle-coated filter paper (Ag NPs paper) as a substrate for nanoparticle-enhanced LIBS (NELIBS) to improve the quantitative detection of K. First, the preparation process of the Ag NPs paper substrate was systematically optimized. The optimal K detection signal was obtained with the Ag NPs paper substrate treated with 1.5 mol/L NaCl and colloidal Ag NPs at neutral pH. Then, the optimized Ag NPs paper was employed for quantitative determination of K in potassium-chloride (KCl) aqueous solution and fetal bovine serum (FBS), including hypokalemia, hyperkalemia, and normal potassium levels. Under these conditions, the limit of detection (LoD) of NELIBS for K was lower than that of normal LIBS, decreasing from 2.29 mmol/L (89.3 mg/L) to 0.81 mmol/L (31.6 mg/L) in KCl aqueous solution and from 0.96 mmol/L (37.4 mg/L) to 0.32 mmol/L (12.5 mg/L) in FBS, respectively. It also enabled reliable discrimination of concentration changes as small as 0.5 mmol/L. These findings highlight the feasibility of NELIBS for sensitive and accurate detection of electrolyte elements in complex biological samples, offering promising prospects for clinical diagnostics.
{"title":"Ag NP-coated filter paper as a nanoparticle-enhanced laser-induced breakdown spectroscopy substrate for quantitative detection of potassium","authors":"Xinxin Zhang , Yumeng Yuan , Zihao Guo , Xue Chen , Xiaohui Li","doi":"10.1016/j.sab.2025.107386","DOIUrl":"10.1016/j.sab.2025.107386","url":null,"abstract":"<div><div>Accurate monitoring of serum potassium (K) levels is essential for clinical diagnostics due to their vital roles in maintaining physiological functions. Although laser-induced breakdown spectroscopy (LIBS) enables rapid elemental analysis, its limited sensitivity and precision restrict its effectiveness in quantifying K in complex biological samples. This study explores the application of silver nanoparticle-coated filter paper (Ag NPs paper) as a substrate for nanoparticle-enhanced LIBS (NELIBS) to improve the quantitative detection of K. First, the preparation process of the Ag NPs paper substrate was systematically optimized. The optimal K detection signal was obtained with the Ag NPs paper substrate treated with 1.5 mol/L NaCl and colloidal Ag NPs at neutral pH. Then, the optimized Ag NPs paper was employed for quantitative determination of K in potassium-chloride (KCl) aqueous solution and fetal bovine serum (FBS), including hypokalemia, hyperkalemia, and normal potassium levels. Under these conditions, the limit of detection (LoD) of NELIBS for K was lower than that of normal LIBS, decreasing from 2.29 mmol/L (89.3 mg/L) to 0.81 mmol/L (31.6 mg/L) in KCl aqueous solution and from 0.96 mmol/L (37.4 mg/L) to 0.32 mmol/L (12.5 mg/L) in FBS, respectively. It also enabled reliable discrimination of concentration changes as small as 0.5 mmol/L. These findings highlight the feasibility of NELIBS for sensitive and accurate detection of electrolyte elements in complex biological samples, offering promising prospects for clinical diagnostics.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107386"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145466866","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: 2025-10-29DOI: 10.1016/j.sab.2025.107377
Mattia Massa , Elisa Galli , Alessandra Zanoletti , Annalisa Zacco , Silvana De Iuliis , Laura Eleonora Depero , Vincenzo Palleschi , Laura Borgese , Elza Bontempi
Sewage sludge ash (SSA), derived from the incineration of wastewater treatment sludge, typically contains phosphorus concentrations ranging from 4 % to 12 % by weight. This significant P content makes SSA a promising secondary resource, particularly for applications such as fertilizer production. In this study, we explore the feasibility of using handheld Laser-Induced Breakdown Spectroscopy (LIBS) for the rapid and direct determination of phosphorus content in SSA samples. The proposed method enables rapid and accurate quantification of phosphorus with minimal sample preparation and demonstrates strong resilience to matrix effects, which often compromise the reliability of conventional LIBS analysis.
The approach is based on a Convolutional Neural Network (CNN), designed to produce a single calibration model capable of addressing the wide variability in phosphorus concentration typically observed in SSA samples. The innovative aspect of this work is the complete separation of the training stage of the CNN, which is done using simple synthetic reference samples, from the validation, which involves actual SSA samples collected from a waste-to-energy power plant, previously characterized using standard laboratory methods. This procedure allows to select, among the many spectral features that can be used for modelling the training set, only the ones that are proven to effectively work for the determination of phosphorous concentration in the SSA samples, which have a much more complex composition with respect to the synthetic training samples.
In addition to presenting this novel methodology, the study also includes a discussion of alternative approaches reported in the literature for matrix-independent quantitative LIBS analysis of phosphorus. This comparative overview highlights the advantages of the proposed method for in-situ analysis of SSA.
{"title":"Overcoming matrix effects on the determination of phosphorus concentration in sewage sludge ash using laser-induced breakdown spectroscopy hand-held instrumentation","authors":"Mattia Massa , Elisa Galli , Alessandra Zanoletti , Annalisa Zacco , Silvana De Iuliis , Laura Eleonora Depero , Vincenzo Palleschi , Laura Borgese , Elza Bontempi","doi":"10.1016/j.sab.2025.107377","DOIUrl":"10.1016/j.sab.2025.107377","url":null,"abstract":"<div><div>Sewage sludge ash (SSA), derived from the incineration of wastewater treatment sludge, typically contains phosphorus concentrations ranging from 4 % to 12 % by weight. This significant P content makes SSA a promising secondary resource, particularly for applications such as fertilizer production. In this study, we explore the feasibility of using handheld Laser-Induced Breakdown Spectroscopy (LIBS) for the rapid and direct determination of phosphorus content in SSA samples. The proposed method enables rapid and accurate quantification of phosphorus with minimal sample preparation and demonstrates strong resilience to matrix effects, which often compromise the reliability of conventional LIBS analysis.</div><div>The approach is based on a Convolutional Neural Network (CNN), designed to produce a single calibration model capable of addressing the wide variability in phosphorus concentration typically observed in SSA samples. The innovative aspect of this work is the complete separation of the training stage of the CNN, which is done using simple synthetic reference samples, from the validation, which involves actual SSA samples collected from a waste-to-energy power plant, previously characterized using standard laboratory methods. This procedure allows to select, among the many spectral features that can be used for modelling the training set, only the ones that are proven to effectively work for the determination of phosphorous concentration in the SSA samples, which have a much more complex composition with respect to the synthetic training samples.</div><div>In addition to presenting this novel methodology, the study also includes a discussion of alternative approaches reported in the literature for matrix-independent quantitative LIBS analysis of phosphorus. This comparative overview highlights the advantages of the proposed method for in-situ analysis of SSA.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107377"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145466865","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: 2025-11-04DOI: 10.1016/j.sab.2025.107382
Andrey Zhirkov, Vladimir Yagov
The metrological characteristics of drop-spark optical emission spectrometry determination of Ag with anode sampling were established. The influence of a wide range of organic and inorganic compounds has been studied. The application of 0.15 M ammonia background solution is shown to provide maximum analysis sensitivity and increases possible range of sample types due to tolerance to chloride. Under these optimal conditions, the detection limit is 1 ppb, and the linear calibration range is 3 orders of magnitude. The developed procedure was successfully applied in the Ag determination in copper electrical cable (9.5 ppm) and antiquarian copper coin (0.14% wt.).
{"title":"Drop-spark discharge atomic emission determination of silver with a liquid anode sample introduction: Analytical possibilities and unusual matrix interferences","authors":"Andrey Zhirkov, Vladimir Yagov","doi":"10.1016/j.sab.2025.107382","DOIUrl":"10.1016/j.sab.2025.107382","url":null,"abstract":"<div><div>The metrological characteristics of drop-spark optical emission spectrometry determination of Ag with anode sampling were established. The influence of a wide range of organic and inorganic compounds has been studied. The application of 0.15 M ammonia background solution is shown to provide maximum analysis sensitivity and increases possible range of sample types due to tolerance to chloride. Under these optimal conditions, the detection limit is 1 ppb, and the linear calibration range is 3 orders of magnitude. The developed procedure was successfully applied in the Ag determination in copper electrical cable (9.5 ppm) and antiquarian copper coin (0.14% wt.).</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107382"},"PeriodicalIF":3.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145466864","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 : 2025-12-01Epub Date: 2025-09-25DOI: 10.1016/j.sab.2025.107338
C. Collet , A. Cousin , O. Beyssac , P. Beck , O. Forni , S. Clegg , J. Comellas , E. Clavé , A. Fau , S. Pont , F. Poulet , R.K. Martinez , H. Austrheim , S. Maurice , R.C. Wiens
The NASA Perseverance rover is exploring Jezero crater on Mars since February 2021. Orbital data from Nili Fossae and Jezero crater show a wide diversity of mineralogical signatures including primary mineral like olivine as well as diverse secondary minerals like clays and serpentines and one of the strongest spectral signatures of carbonate on Mars from orbit. This olivine and carbonate-bearing unit is regionally extensive. Most of the studies interpreted the relationship between olivine and carbonate-bearing units as a result of weathering processes involving fluid–rock interactions such as serpentinization and carbonation. Since February 2021, Perseverance has confirmed this large diversity of primary and secondary minerals. The detection of serpentine is of particular interest in order to better constrain the past environment at Jezero crater. Among the science payload, SuperCam is combining three spectral techniques (Laser-Induced Breakdown Spectroscopy - LIBS, Raman, and Visible and near InfraRed - VISIR) that give access to the elemental composition of the targets but also to their mineral and molecular structure. Here, we use terrestrial ultramafic rocks with various degrees of alteration that were well characterized from previous studies, and we analyze them with SuperCam replicate laboratory setups to investigate the sensitivity of SuperCam to detect olivine and secondary phases, in particular serpentines. Distinguishing serpentine from olivine by LIBS is challenging since they have similar chemistry. On the other hand, Raman spectroscopy is able to detect all the phases present in the analyzed samples, when their content is high enough. Finally, the VISIR technique detected the secondary phases while it did not observe easily the olivine. We found that the synergy between these three techniques is of particular importance to differentiate such specific phases, which occur as intricate mixtures down to the sub-micrometer scale in natural targets.
{"title":"Variably weathered ultramafic rocks: Investigation of their mineralogy with SuperCam-like techniques","authors":"C. Collet , A. Cousin , O. Beyssac , P. Beck , O. Forni , S. Clegg , J. Comellas , E. Clavé , A. Fau , S. Pont , F. Poulet , R.K. Martinez , H. Austrheim , S. Maurice , R.C. Wiens","doi":"10.1016/j.sab.2025.107338","DOIUrl":"10.1016/j.sab.2025.107338","url":null,"abstract":"<div><div>The NASA Perseverance rover is exploring Jezero crater on Mars since February 2021. Orbital data from Nili Fossae and Jezero crater show a wide diversity of mineralogical signatures including primary mineral like olivine as well as diverse secondary minerals like clays and serpentines and one of the strongest spectral signatures of carbonate on Mars from orbit. This olivine and carbonate-bearing unit is regionally extensive. Most of the studies interpreted the relationship between olivine and carbonate-bearing units as a result of weathering processes involving fluid–rock interactions such as serpentinization and carbonation. Since February 2021, Perseverance has confirmed this large diversity of primary and secondary minerals. The detection of serpentine is of particular interest in order to better constrain the past environment at Jezero crater. Among the science payload, SuperCam is combining three spectral techniques (Laser-Induced Breakdown Spectroscopy - LIBS, Raman, and Visible and near InfraRed - VISIR) that give access to the elemental composition of the targets but also to their mineral and molecular structure. Here, we use terrestrial ultramafic rocks with various degrees of alteration that were well characterized from previous studies, and we analyze them with SuperCam replicate laboratory setups to investigate the sensitivity of SuperCam to detect olivine and secondary phases, in particular serpentines. Distinguishing serpentine from olivine by LIBS is challenging since they have similar chemistry. On the other hand, Raman spectroscopy is able to detect all the phases present in the analyzed samples, when their content is high enough. Finally, the VISIR technique detected the secondary phases while it did not observe easily the olivine. We found that the synergy between these three techniques is of particular importance to differentiate such specific phases, which occur as intricate mixtures down to the sub-micrometer scale in natural targets.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107338"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227389","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 : 2025-12-01Epub Date: 2025-09-21DOI: 10.1016/j.sab.2025.107340
Shoujie Li , Zixiong Qin , Jingjun Lin , Lihui Ren , Yuan Lu , Zhenzhen Wang , Ronger Zheng , Yoshihiro Deguchi
The elemental microanalysis plays a crucial role in gray cast iron quality control, and segregation monitoring is an essential step in this analysis. In this study, we developed a three-dimensional laser-induced breakdown spectroscopy (3D LIBS) system for examining gray cast iron using a 9 ps-pulsed laser operating at 355 nm. 2 μm high spatial-resolved measurements were successfully achieved to determine the 3D segregation of Copper (Cu), and Manganese (Mn). In terms of experimental methodology, this study has overcome the limitations of traditional three-dimensional imaging techniques by abandoning conventional approaches that rely on physical sectioning to acquire depth information. Instead, it adopts a more efficient and non-destructive strategy: performing mapping ablation cleaning under laser defocusing conditions to eliminate interference from surface impurities or previously analyzed regions, followed by 3D LIBS imaging implementation with precisely focused laser beams. Through the ablation theory formulas, the axial ablation depth under laser irradiation was precisely calculated as 2 μm, thereby obtaining a total of 12 layers of depth-resolved data while maintaining stable and reliable signal-to-noise ratios (SNR) for each layer. The microscale 3D LIBS analytical technique provides a powerful tool for understanding the distribution patterns of various segregated elements in gray cast iron materials. Therefore, 3D LIBS has been demonstrated as an effective technology for addressing elemental segregation and can serve as an alternative methodology for gray cast iron quality inspection.
{"title":"3D microanalysis of iron segregation based on picosecond laser-induced breakdown spectroscopy imaging","authors":"Shoujie Li , Zixiong Qin , Jingjun Lin , Lihui Ren , Yuan Lu , Zhenzhen Wang , Ronger Zheng , Yoshihiro Deguchi","doi":"10.1016/j.sab.2025.107340","DOIUrl":"10.1016/j.sab.2025.107340","url":null,"abstract":"<div><div>The elemental microanalysis plays a crucial role in gray cast iron quality control, and segregation monitoring is an essential step in this analysis. In this study, we developed a three-dimensional laser-induced breakdown spectroscopy (3D LIBS) system for examining gray cast iron using a 9 ps-pulsed laser operating at 355 nm. 2 μm high spatial-resolved measurements were successfully achieved to determine the 3D segregation of Copper (Cu), and Manganese (Mn). In terms of experimental methodology, this study has overcome the limitations of traditional three-dimensional imaging techniques by abandoning conventional approaches that rely on physical sectioning to acquire depth information. Instead, it adopts a more efficient and non-destructive strategy: performing mapping ablation cleaning under laser defocusing conditions to eliminate interference from surface impurities or previously analyzed regions, followed by 3D LIBS imaging implementation with precisely focused laser beams. Through the ablation theory formulas, the axial ablation depth under laser irradiation was precisely calculated as 2 μm, thereby obtaining a total of 12 layers of depth-resolved data while maintaining stable and reliable signal-to-noise ratios (SNR) for each layer. The microscale 3D LIBS analytical technique provides a powerful tool for understanding the distribution patterns of various segregated elements in gray cast iron materials. Therefore, 3D LIBS has been demonstrated as an effective technology for addressing elemental segregation and can serve as an alternative methodology for gray cast iron quality inspection.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107340"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145158212","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 : 2025-12-01Epub Date: 2025-09-11DOI: 10.1016/j.sab.2025.107337
J. Manrique , D.M. Díaz Pace , J.A. Aguilera , C. Aragón
Stark widths and shifts of Nb II spectral lines have been measured by laser-induced breakdown spectroscopy (LIBS). The experimental line profiles are obtained from spectra of the emission of laser-induced plasmas generated with samples prepared by borate fusion with small niobium concentrations, selected to minimize self-absorption. Using different time delays in the detection of the emission, electron densities ranging from 0.81 × 1017 cm−3 to 6.7 × 1017 cm−3 and temperatures in the interval 10,100–16,700 K are employed in each measurement. The 26 Stark widths and 22 Stark shifts determined include spectral lines from transitions between 10 multiplets and 3 configurations. To our knowledge, only two experimental data for Nb II Stark widths were available previously in the literature.
用激光诱导击穿光谱（LIBS）测量了铌II谱线的斯塔克宽度和位移。实验谱线是从激光诱导等离子体的发射光谱中获得的，这些等离子体是由硼酸盐与小铌浓度融合制备的样品产生的，选择最小的自吸收。利用不同的探测延迟时间，电子密度在0.81 × 1017 cm−3到6.7 × 1017 cm−3之间，温度在10,100-16,700 K之间。确定的26个斯塔克宽度和22个斯塔克位移包括10个多胞胎和3个构型之间转换的光谱线。据我们所知，在以前的文献中只有两个Nb II Stark宽度的实验数据。
{"title":"Experimental Stark widths and shifts of Nb II spectral lines","authors":"J. Manrique , D.M. Díaz Pace , J.A. Aguilera , C. Aragón","doi":"10.1016/j.sab.2025.107337","DOIUrl":"10.1016/j.sab.2025.107337","url":null,"abstract":"<div><div>Stark widths and shifts of Nb II spectral lines have been measured by laser-induced breakdown spectroscopy (LIBS). The experimental line profiles are obtained from spectra of the emission of laser-induced plasmas generated with samples prepared by borate fusion with small niobium concentrations, selected to minimize self-absorption. Using different time delays in the detection of the emission, electron densities ranging from 0.81 × 10<sup>17</sup> cm<sup>−3</sup> to 6.7 × 10<sup>17</sup> cm<sup>−3</sup> and temperatures in the interval 10,100–16,700 K are employed in each measurement. The 26 Stark widths and 22 Stark shifts determined include spectral lines from transitions between 10 multiplets and 3 configurations. To our knowledge, only two experimental data for Nb II Stark widths were available previously in the literature.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107337"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061131","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 : 2025-12-01Epub Date: 2025-09-10DOI: 10.1016/j.sab.2025.107336
Guangchun Luo , Chunjiang Zhao , Shixiang Ma , Hongwu Tian , Fengjing Cao , Daming Dong
Heavy metal contamination in water bodies poses a severe threat to ecosystems and human health, thereby necessitating the development of rapid and highly sensitive detection methods. Traditional laboratory detection techniques are limited in their widespread application due to expensive equipment and complex operational procedures. To address this issue, we developed a rapid detection technique based on AuAgPd trimetallic nanoparticles(TNPs)-modified filter paper combined with laser-induced breakdown spectroscopy (LIBS) for the determination of total chromium (Cr) in water. AuAgPdTNPs-modified filter paper efficiently enriches Cr of different valence states, while LIBS quantifies total Cr from its characteristic emission lines. Experimental results demonstrate that the limit of detection (LOD) of total Cr is 0.21 μg/L (4 nM), showing good linearity in the ranges of 0–50 μg/L and 50–1000 μg/L. In tests with actual water samples, the method showed high reliability, with recovery rates ranging from 95.24 % to 106.15 %. This technology provides a novel solution for the rapid detection of heavy metal pollution in water bodies and holds broad application prospects.
{"title":"Rapid detection of total chromium in water bodies using AuAgPd trimetallic nanoparticles-modified filter paper combined with laser-induced breakdown spectroscopy","authors":"Guangchun Luo , Chunjiang Zhao , Shixiang Ma , Hongwu Tian , Fengjing Cao , Daming Dong","doi":"10.1016/j.sab.2025.107336","DOIUrl":"10.1016/j.sab.2025.107336","url":null,"abstract":"<div><div>Heavy metal contamination in water bodies poses a severe threat to ecosystems and human health, thereby necessitating the development of rapid and highly sensitive detection methods. Traditional laboratory detection techniques are limited in their widespread application due to expensive equipment and complex operational procedures. To address this issue, we developed a rapid detection technique based on AuAgPd trimetallic nanoparticles(TNPs)-modified filter paper combined with laser-induced breakdown spectroscopy (LIBS) for the determination of total chromium (Cr) in water. AuAgPdTNPs-modified filter paper efficiently enriches Cr of different valence states, while LIBS quantifies total Cr from its characteristic emission lines. Experimental results demonstrate that the limit of detection (LOD) of total Cr is 0.21 μg/L (4 nM), showing good linearity in the ranges of 0–50 μg/L and 50–1000 μg/L. In tests with actual water samples, the method showed high reliability, with recovery rates ranging from 95.24 % to 106.15 %. This technology provides a novel solution for the rapid detection of heavy metal pollution in water bodies and holds broad application prospects.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107336"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106464","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 : 2025-12-01Epub Date: 2025-09-26DOI: 10.1016/j.sab.2025.107345
Yijun Zhang , Yiwei Chen , Yuhang Zhang , Yan Deng , Jiahan Wang
To address the critical national demand for securing titanium, zirconium, and hafnium resources, an enhanced alkali fusion–ICP-MS analytical method was developed using a lithium metaborate–lithium tetraborate composite flux. This method effectively overcomes the technical challenges posed by the high-salt matrix and refractory minerals commonly found in marine placer deposits from the Hainan coastal region. It enables high-throughput quantification of ten major and trace elements, including Ti, Zr, and Hf, in coastal placer deposits. Validation using certified reference materials across five concentration levels demonstrated excellent accuracy and precision, with relative errors (RE) ≤ 5.5 % and relative standard deviations (RSD) ≤ 5.1 %. The method provides a reliable solution for multi-element batch analysis of complex matrices and offers significant practical value in the assessment and development of marine mineral resources. When applied to the analysis of placer samples from the eastern coastal waters of Hainan Island, the results revealed strong positive correlations among Ti, Zr, and Hf (correlation coefficient r ≥ 0.94), as well as co-enrichment of Mn and V with the major ore-forming elements (r = 0.77–0.85). These findings offer preliminary insights into the metallogenic mechanisms of the region.
{"title":"Determination of ten major and trace elements in coastal placer deposits using composite flux alkali fusion-ICP-MS and analysis of their elemental associations","authors":"Yijun Zhang , Yiwei Chen , Yuhang Zhang , Yan Deng , Jiahan Wang","doi":"10.1016/j.sab.2025.107345","DOIUrl":"10.1016/j.sab.2025.107345","url":null,"abstract":"<div><div>To address the critical national demand for securing titanium, zirconium, and hafnium resources, an enhanced alkali fusion–ICP-MS analytical method was developed using a lithium metaborate–lithium tetraborate composite flux. This method effectively overcomes the technical challenges posed by the high-salt matrix and refractory minerals commonly found in marine placer deposits from the Hainan coastal region. It enables high-throughput quantification of ten major and trace elements, including Ti, Zr, and Hf, in coastal placer deposits. Validation using certified reference materials across five concentration levels demonstrated excellent accuracy and precision, with relative errors (RE) ≤ 5.5 % and relative standard deviations (RSD) ≤ 5.1 %. The method provides a reliable solution for multi-element batch analysis of complex matrices and offers significant practical value in the assessment and development of marine mineral resources. When applied to the analysis of placer samples from the eastern coastal waters of Hainan Island, the results revealed strong positive correlations among Ti, Zr, and Hf (correlation coefficient <em>r</em> ≥ 0.94), as well as co-enrichment of Mn and V with the major ore-forming elements (<em>r</em> = 0.77–0.85). These findings offer preliminary insights into the metallogenic mechanisms of the region.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107345"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227392","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 : 2025-12-01Epub Date: 2025-08-26DOI: 10.1016/j.sab.2025.107314
Fei Chen , Jiahui Liang , Shuqing Wang , Zhihui Tian , Yang Zhao , Yan Zhang , Lei Zhang , Wangbao Yin , Jiaxuan Li , Peihua Zhang , Liantuan Xiao , Suotang Jia
Laser-induced breakdown spectroscopy (LIBS) is widely recognized for its rapid, low-destructive, and real-time elemental analysis capabilities. However, the complexity of bacterial samples and spectral signal interference caused by self-absorption effects present significant challenges to the accuracy and reliability of LIBS for quantitative bacterial concentration analysis. To address these challenges, a novel self-absorption correction method based on doublet line intensity ratios and K-parameter ratios is proposed and, for the first time, successfully applied to improve the accuracy of bacterial concentration quantification. Laser parameters were optimized to verify that the bacterial laser-induced plasma satisfies local thermodynamic equilibrium (LTE). Characteristic doublet lines sharing similar or identical upper and/or lower energy levels (Ca II 393.36/396.84 nm, Ca I 612.22/616.22 nm, and K I 766.49/769.90 nm) were selected to develop a model correlating the K-parameter ratio with the self-absorption coefficient (SA), enabling effective spectral line self-absorption correction. The results show that after self-absorption correction, the quantitative analysis errors were significantly reduced: for Escherichia coli and Bacillus subtilis, the errors decreased by 4.0 % and 11.6 % using Ca II 393.36 nm, 9.1 % and 6.9 % using K I 766.49 nm, and 4.3 % and 3.9 % using Ca I 612.22 nm, respectively. Accurate quantification was achieved within the bacterial concentration range of 107 to 108 CFU/mL. This correction method is straightforward, efficient, and independent of complex parameters or external conditions, significantly improving the precision and reproducibility of LIBS in bacterial concentration analysis. Additionally, the SVM-based classification accuracy for the five bacterial species improved markedly, rising by 3.55 %. Its robust generalizability supports its extension to other microbial detection applications, providing a rapid, accurate, and cost-effective approach. These findings lay a solid foundation for broader LIBS applications in biological monitoring, with promising potential in environmental surveillance, food safety, and public health diagnostics.
激光诱导击穿光谱（LIBS）因其快速、低破坏性和实时的元素分析能力而得到广泛认可。然而，细菌样品的复杂性和自吸收效应引起的光谱信号干扰对LIBS用于细菌浓度定量分析的准确性和可靠性提出了重大挑战。为了解决这些问题，本文提出了一种基于双线强度比和k参数比的自吸收校正方法，并首次成功应用于提高细菌浓度定量的准确性。通过优化激光参数，验证了细菌激光诱导等离子体满足局部热力学平衡（LTE）。选择具有相似或相同的上下能级（Ca II 393.36/396.84 nm, Ca I 612.22/616.22 nm和K I 766.49/769.90 nm）的特征双线，建立K参数比与自吸收系数（SA）的关联模型，实现有效的谱线自吸收校正。结果表明，经自吸收校正后，对大肠杆菌和枯草芽孢杆菌的定量分析误差显著降低，Ca II 393.36 nm的误差分别降低4.0%和11.6%,K I 766.49 nm的误差分别降低9.1%和6.9%,Ca I 612.22 nm的误差分别降低4.3%和3.9%。在107 ~ 108 CFU/mL的细菌浓度范围内实现准确定量。该校正方法简单、高效，不受复杂参数和外部条件的影响，显著提高了LIBS在细菌浓度分析中的精密度和重现性。此外，基于svm的5种细菌的分类准确率显著提高，提高了3.55%。其强大的通用性支持其扩展到其他微生物检测应用，提供快速，准确和具有成本效益的方法。这些发现为LIBS在生物监测中的广泛应用奠定了坚实的基础，在环境监测、食品安全和公共卫生诊断方面具有广阔的应用前景。
{"title":"Doublet line ratio-based self-absorption correction in LIBS applied to bacterial concentration quantification","authors":"Fei Chen , Jiahui Liang , Shuqing Wang , Zhihui Tian , Yang Zhao , Yan Zhang , Lei Zhang , Wangbao Yin , Jiaxuan Li , Peihua Zhang , Liantuan Xiao , Suotang Jia","doi":"10.1016/j.sab.2025.107314","DOIUrl":"10.1016/j.sab.2025.107314","url":null,"abstract":"<div><div>Laser-induced breakdown spectroscopy (LIBS) is widely recognized for its rapid, low-destructive, and real-time elemental analysis capabilities. However, the complexity of bacterial samples and spectral signal interference caused by self-absorption effects present significant challenges to the accuracy and reliability of LIBS for quantitative bacterial concentration analysis. To address these challenges, a novel self-absorption correction method based on doublet line intensity ratios and K-parameter ratios is proposed and, for the first time, successfully applied to improve the accuracy of bacterial concentration quantification. Laser parameters were optimized to verify that the bacterial laser-induced plasma satisfies local thermodynamic equilibrium (LTE). Characteristic doublet lines sharing similar or identical upper and/or lower energy levels (Ca II 393.36/396.84 nm, Ca I 612.22/616.22 nm, and K I 766.49/769.90 nm) were selected to develop a model correlating the K-parameter ratio with the self-absorption coefficient (SA), enabling effective spectral line self-absorption correction. The results show that after self-absorption correction, the quantitative analysis errors were significantly reduced: for <em>Escherichia coli</em> and <em>Bacillus subtilis</em>, the errors decreased by 4.0 % and 11.6 % using Ca II 393.36 nm, 9.1 % and 6.9 % using K I 766.49 nm, and 4.3 % and 3.9 % using Ca I 612.22 nm, respectively. Accurate quantification was achieved within the bacterial concentration range of 10<sup>7</sup> to 10<sup>8</sup> CFU/mL. This correction method is straightforward, efficient, and independent of complex parameters or external conditions, significantly improving the precision and reproducibility of LIBS in bacterial concentration analysis. Additionally, the SVM-based classification accuracy for the five bacterial species improved markedly, rising by 3.55 %. Its robust generalizability supports its extension to other microbial detection applications, providing a rapid, accurate, and cost-effective approach. These findings lay a solid foundation for broader LIBS applications in biological monitoring, with promising potential in environmental surveillance, food safety, and public health diagnostics.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107314"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933796","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-09-22DOI: 10.1016/j.sab.2025.107341
Xiaoxi Chen , Ran Hai , Yaoxing Wu , Hongbin Ding
The annular–point double pulse laser-induced breakdown spectroscopy (DP-LIBS) is an effective way of significantly enhancing plasma parameters to amplify the spectral emission intensity for analysis of co-deposition layers in fusion devices. A two-dimensional numerical model, describing laser–material interaction, vapor plume expansion, plasma formation and laser–plasma interaction at a pressure of 10−4 mbar, was applied to investigate spatial and temporal evolutions of laser-induced boron plasma using annular–point double pulse configuration, which is crucial for analytical capabilities of LIBS techniques. The annular-point double pulse configuration demonstrated significant enhancement in plasma temperature compared to conventional single pulse configuration, under the same laser energy and laser fluence. At a laser fluence of 18 J/cm2, we examined a series of inter-pulse delay times and found that the 20 ns delay time exhibited optimal performance, maintaining electron temperatures exceeding 2.5 eV for extended periods after the second pulse. Quantitatively, this optimal configuration achieved electron temperatures approximately 1.7–2.2 times as high as those in single-pulse configuration and maintained electron densities in the 1016–1017 cm−3 range. The temperature enhancement resulted from the collision between the annular pre-pulse plasma and the subsequent point pulse plasma, forming a well-defined stagnation layer.
{"title":"Numerical simulation of spatial and temporal evolution of laser-induced boron plasma using annular-point double pulse configuration","authors":"Xiaoxi Chen , Ran Hai , Yaoxing Wu , Hongbin Ding","doi":"10.1016/j.sab.2025.107341","DOIUrl":"10.1016/j.sab.2025.107341","url":null,"abstract":"<div><div>The annular–point double pulse laser-induced breakdown spectroscopy (DP-LIBS) is an effective way of significantly enhancing plasma parameters to amplify the spectral emission intensity for analysis of co-deposition layers in fusion devices. A two-dimensional numerical model, describing laser–material interaction, vapor plume expansion, plasma formation and laser–plasma interaction at a pressure of 10<sup>−4</sup> mbar, was applied to investigate spatial and temporal evolutions of laser-induced boron plasma using annular–point double pulse configuration, which is crucial for analytical capabilities of LIBS techniques. The annular-point double pulse configuration demonstrated significant enhancement in plasma temperature compared to conventional single pulse configuration, under the same laser energy and laser fluence. At a laser fluence of 18 J/cm<sup>2</sup>, we examined a series of inter-pulse delay times and found that the 20 ns delay time exhibited optimal performance, maintaining electron temperatures exceeding 2.5 eV for extended periods after the second pulse. Quantitatively, this optimal configuration achieved electron temperatures approximately 1.7–2.2 times as high as those in single-pulse configuration and maintained electron densities in the 10<sup>16</sup>–10<sup>17</sup> cm<sup>−3</sup> range. The temperature enhancement resulted from the collision between the annular pre-pulse plasma and the subsequent point pulse plasma, forming a well-defined stagnation layer.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107341"},"PeriodicalIF":3.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227387","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}
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