Pub Date : 2026-01-07DOI: 10.1016/j.sab.2026.107451
Hannah Juan Han , Alexander P. Gysi , Bonnie Frey
Inductively coupled plasma techniques such as ICP-OES and ICP-MS are routinely used to determine the concentrations of rare earth elements (REE) in water samples. However, their performance for the determination of REE concentration in mine drainage waters from epithermal vein and porphyry copper mining districts has not been evaluated extensively. In this work, we develop an REE analysis method on an Agilent 5900 ICP-OES instrument and assess the accuracy and precision for the quantification of REE in the natural waters collected from mine adits and an acid seep of mine sites in the Steeple Rock and Hillsboro mining districts, New Mexico, USA. The total REE concentrations in the water samples were measured using the methods we developed for both ICP-OES and ICP-MS. The power of the new ICP-OES method lies in routine analysis of μg/L level concentrations normally analyzed using ICP-MS, including a U.S. Geological Survey standard reference sample, laboratory blank samples spiked with a National Institute of Standards and Technology traceable standard, and surface water samples from mine waste sites. This ICP-OES method achieves low quantification limits ranging from 0.2 to 5 μg/L and excellent analytical accuracy and precision for REE analysis. The precision of light (La-Gd) and heavy (Tb-Lu) REE analysis using this method are better than 5% at average concentrations above 5 ± 4 μg/L and 3 ± 2 μg/L, respectively, and 3% at average concentrations above 10 ± 9 μg/L and 5 ± 4 μg/L, respectively. This method also shows excellent sensitivity and reproducibility for our laboratory and field samples.
{"title":"An ICP-OES method for the precise and accurate quantification of rare earth elements in natural water: A comparative study from mine waste sites in New Mexico, USA","authors":"Hannah Juan Han , Alexander P. Gysi , Bonnie Frey","doi":"10.1016/j.sab.2026.107451","DOIUrl":"10.1016/j.sab.2026.107451","url":null,"abstract":"<div><div>Inductively coupled plasma techniques such as ICP-OES and ICP-MS are routinely used to determine the concentrations of rare earth elements (REE) in water samples. However, their performance for the determination of REE concentration in mine drainage waters from epithermal vein and porphyry copper mining districts has not been evaluated extensively. In this work, we develop an REE analysis method on an Agilent 5900 ICP-OES instrument and assess the accuracy and precision for the quantification of REE in the natural waters collected from mine adits and an acid seep of mine sites in the Steeple Rock and Hillsboro mining districts, New Mexico, USA. The total REE concentrations in the water samples were measured using the methods we developed for both ICP-OES and ICP-MS. The power of the new ICP-OES method lies in routine analysis of μg/L level concentrations normally analyzed using ICP-MS, including a U.S. Geological Survey standard reference sample, laboratory blank samples spiked with a National Institute of Standards and Technology traceable standard, and surface water samples from mine waste sites. This ICP-OES method achieves low quantification limits ranging from 0.2 to 5 μg/L and excellent analytical accuracy and precision for REE analysis. The precision of light (La-Gd) and heavy (Tb-Lu) REE analysis using this method are better than 5% at average concentrations above 5 ± 4 μg/L and 3 ± 2 μg/L, respectively, and 3% at average concentrations above 10 ± 9 μg/L and 5 ± 4 μg/L, respectively. This method also shows excellent sensitivity and reproducibility for our laboratory and field samples.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107451"},"PeriodicalIF":3.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976803","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 : 2026-01-06DOI: 10.1016/j.sab.2025.107449
Sabrina Molinaro , Roberta Zanini , Kalliopi Tsampa , Elti Cattaruzza , Andreas G. Karydas , Arianna Traviglia
This study aims to assess the reliability of micro-X-ray fluorescence spectroscopy (μ-XRF) as a quantitative, non-invasive tool for the in-situ compositional analysis of ancient glass. μ-XRF is widely employed in archaeological and materials science contexts due to its ability to rapidly detect major, minor, and trace elements without the need for sampling. However, it is often assumed that its limited sensitivity to light elements (Z < 13) in field applications poses challenges for a comprehensive characterisation of glass-making technologies and raw materials. In this study, we evaluate the analytical performance of μ-XRF for glass analysis, going beyond compositional characterisation by systematically comparing it with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LA-ICP-MS offers superior detection limits and a broader elemental range, but its use is constrained by the need for sample preparation and its non-portable nature. The precision of μ-XRF was assessed through repeated daily measurements, while accuracy was evaluated using the certified reference glasses Corning A and B. Correction trends were developed by comparing μ-XRF results with both the nominal concentrations of these standards and with corresponding LA-ICP-MS data, in order to mitigate inherent limitations and enhance the method's reliability. The validated protocol was then applied to a set of Roman glass samples of unknown composition. The results confirm that, despite its limitations, μ-XRF can deliver accurate and reproducible data, supporting its use as a rapid and versatile method for in-situ compositional analysis of ancient glass.
{"title":"Evaluating analytical methods for ancient glass: Validation of micro-XRF quantitative data through comparison with LA-ICP-MS","authors":"Sabrina Molinaro , Roberta Zanini , Kalliopi Tsampa , Elti Cattaruzza , Andreas G. Karydas , Arianna Traviglia","doi":"10.1016/j.sab.2025.107449","DOIUrl":"10.1016/j.sab.2025.107449","url":null,"abstract":"<div><div>This study aims to assess the reliability of micro-X-ray fluorescence spectroscopy (μ-XRF) as a quantitative, non-invasive tool for the <em>in-situ</em> compositional analysis of ancient glass. μ-XRF is widely employed in archaeological and materials science contexts due to its ability to rapidly detect major, minor, and trace elements without the need for sampling. However, it is often assumed that its limited sensitivity to light elements (Z < 13) in field applications poses challenges for a comprehensive characterisation of glass-making technologies and raw materials. In this study, we evaluate the analytical performance of μ-XRF for glass analysis, going beyond compositional characterisation by systematically comparing it with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LA-ICP-MS offers superior detection limits and a broader elemental range, but its use is constrained by the need for sample preparation and its non-portable nature. The precision of μ-XRF was assessed through repeated daily measurements, while accuracy was evaluated using the certified reference glasses Corning A and B. Correction trends were developed by comparing μ-XRF results with both the nominal concentrations of these standards and with corresponding LA-ICP-MS data, in order to mitigate inherent limitations and enhance the method's reliability. The validated protocol was then applied to a set of Roman glass samples of unknown composition. The results confirm that, despite its limitations, μ-XRF can deliver accurate and reproducible data, supporting its use as a rapid and versatile method for <em>in-situ</em> compositional analysis of ancient glass.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107449"},"PeriodicalIF":3.8,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976906","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 : 2025-12-29DOI: 10.1016/j.sab.2025.107448
Bing Lu , Haibo He , Zhanjian Lin , Xufeng Wang , Can Hu , Jianfei Xing , Mingsheng Li , Long Wang , Shiping Zhu , Xiangyou Li
Rapid measurement of total phosphorus content in sandy loam soil is of great significance for the accurate management of phosphorus fertilizer in facility vegetable planting. Laser-induced breakdown spectroscopy (LIBS) is a simple and rapid optical detection technique, which has great potential in the rapid analysis of soil components. However, the variations in the composition and structure of the soil matrix can lead to changes in the correlation between characteristic spectral lines and the matrix composition, thereby reducing analytical reliability and limiting the effectiveness of LIBS for rapid soil component assessment. In this study, the LIBS univariate calibration model, LIBS multivariate model and laser-induced breakdown spectroscopy assisted by laser-induced fluorescence (LIBS-LIF) univariate calibration model were used to conduct a rapid detection study on the total phosphorus content of facility sandy loam soil. The results showed that the determination coefficients of the optimal model constructed by LIBS univariate calibration curve, LIBS multivariate modeling and LIBS-LIF univariate calibration curve were 0.6028, 0.9508 and 0.9833, respectively, and the corresponding root mean square errors were 897 mg/kg, 134 mg/kg and 104 mg/kg, respectively. The optimal LIBS-LIF calibration model was externally verified by sampling actual samples. The verification results showed that LIBS-LIF had excellent detection performance, and its determination coefficient and root mean square error were 0.9664 and 130 mg/kg, respectively. In conclusion, LIBS-LIF could eliminate the interference of matrix changes on the detection of total phosphorus in facility sandy loam soil to the greatest extent, and the LIBS-LIF calibration model based on P I 213.62 nm spectral line data would realize the rapid detection and analysis of total phosphorus in facility sandy loam soil. This study would provide a reference for the rapid detection of facility soil with complex matrix compositions.
{"title":"Detection performance comparison of laser-induced breakdown spectroscopy and laser-induced breakdown spectroscopy assisted by laser-induced fluorescence for analysis of total phosphorus in facility sandy loam soil","authors":"Bing Lu , Haibo He , Zhanjian Lin , Xufeng Wang , Can Hu , Jianfei Xing , Mingsheng Li , Long Wang , Shiping Zhu , Xiangyou Li","doi":"10.1016/j.sab.2025.107448","DOIUrl":"10.1016/j.sab.2025.107448","url":null,"abstract":"<div><div>Rapid measurement of total phosphorus content in sandy loam soil is of great significance for the accurate management of phosphorus fertilizer in facility vegetable planting. Laser-induced breakdown spectroscopy (LIBS) is a simple and rapid optical detection technique, which has great potential in the rapid analysis of soil components. However, the variations in the composition and structure of the soil matrix can lead to changes in the correlation between characteristic spectral lines and the matrix composition, thereby reducing analytical reliability and limiting the effectiveness of LIBS for rapid soil component assessment. In this study, the LIBS univariate calibration model, LIBS multivariate model and laser-induced breakdown spectroscopy assisted by laser-induced fluorescence (LIBS-LIF) univariate calibration model were used to conduct a rapid detection study on the total phosphorus content of facility sandy loam soil. The results showed that the determination coefficients of the optimal model constructed by LIBS univariate calibration curve, LIBS multivariate modeling and LIBS-LIF univariate calibration curve were 0.6028, 0.9508 and 0.9833, respectively, and the corresponding root mean square errors were 897 mg/kg, 134 mg/kg and 104 mg/kg, respectively. The optimal LIBS-LIF calibration model was externally verified by sampling actual samples. The verification results showed that LIBS-LIF had excellent detection performance, and its determination coefficient and root mean square error were 0.9664 and 130 mg/kg, respectively. In conclusion, LIBS-LIF could eliminate the interference of matrix changes on the detection of total phosphorus in facility sandy loam soil to the greatest extent, and the LIBS-LIF calibration model based on P I 213.62 nm spectral line data would realize the rapid detection and analysis of total phosphorus in facility sandy loam soil. This study would provide a reference for the rapid detection of facility soil with complex matrix compositions.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107448"},"PeriodicalIF":3.8,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924768","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 : 2025-12-28DOI: 10.1016/j.sab.2025.107447
Mingrui Li , Chunjing Hao , Y.C. Francis Thio , Xuanying Guo , Yarong Zhang , Dechao Yu
Hypersonic plasma jets in Plasma Jet Driven Magneto-Inertial Fusion (PJMIF) require precise real-time diagnostics to optimize transient plasma conditions. In PJMIF, a spherical plasma liner is formed by the merging of a spherical array of plasma jets. The efficacy of a plasma liner in imploding a magnetized target plasma highly depends on its initial temperature, and thus on the temperature of the plasma jets that are used to form the plasma liner. The lower the temperature the higher the implosion efficacy. Traditional Boltzmann plot methods using ordinary least squares (OLS) regression face challenges in quantifying uncertainties and handling heteroscedastic spectral data for single-shot experiments. This study introduces a refined diagnostic framework integrating weighted least squares (WLS) regression, automated outlier rejection, and Bayesian Markov Chain Monte Carlo (MCMC) inversion in a first spectroscopic measurement of the temperature of a plasma jet launched from a PJMIF-class plasma gun. Experimental validation using the ShanghaiTECH Gun #1 (named STG1) plasma gun demonstrated that WLS reduced the 95 % confidence interval by 48 % compared to OLS, achieving sub-0.1 eV precision. Bayesian MCMC further constrained uncertainties, yielding consistent results with auxiliary diagnostics. Additionally, repeated experiments show agreement within ∼3 % between measurements from opposite chords at a 5 mm spatial resolution, confirming macroscopic axial symmetry relevant to PJMIF, and achieving the high collisionality targeted in the STG1 plasma gun design. These advancements provide a robust foundation for real-time, single-shot plasma diagnostics and the optimization of plasma compression in fusion applications.
{"title":"Spectroscopic measurement of the electron temperature of a hypersonic plasma jet","authors":"Mingrui Li , Chunjing Hao , Y.C. Francis Thio , Xuanying Guo , Yarong Zhang , Dechao Yu","doi":"10.1016/j.sab.2025.107447","DOIUrl":"10.1016/j.sab.2025.107447","url":null,"abstract":"<div><div>Hypersonic plasma jets in Plasma Jet Driven Magneto-Inertial Fusion (PJMIF) require precise real-time diagnostics to optimize transient plasma conditions. In PJMIF, a spherical plasma liner is formed by the merging of a spherical array of plasma jets. The efficacy of a plasma liner in imploding a magnetized target plasma highly depends on its initial temperature, and thus on the temperature of the plasma jets that are used to form the plasma liner. The lower the temperature the higher the implosion efficacy. Traditional Boltzmann plot methods using ordinary least squares (OLS) regression face challenges in quantifying uncertainties and handling heteroscedastic spectral data for single-shot experiments. This study introduces a refined diagnostic framework integrating weighted least squares (WLS) regression, automated outlier rejection, and Bayesian Markov Chain Monte Carlo (MCMC) inversion in a first spectroscopic measurement of the temperature of a plasma jet launched from a PJMIF-class plasma gun. Experimental validation using the ShanghaiTECH Gun #1 (named STG1) plasma gun demonstrated that WLS reduced the 95 % confidence interval by 48 % compared to OLS, achieving sub-0.1 eV precision. Bayesian MCMC further constrained uncertainties, yielding consistent results with auxiliary diagnostics. Additionally, repeated experiments show agreement within ∼3 % between measurements from opposite chords at a 5 mm spatial resolution, confirming macroscopic axial symmetry relevant to PJMIF, and achieving the high collisionality targeted in the STG1 plasma gun design. These advancements provide a robust foundation for real-time, single-shot plasma diagnostics and the optimization of plasma compression in fusion applications.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107447"},"PeriodicalIF":3.8,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883999","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 : 2025-12-24DOI: 10.1016/j.sab.2025.107357
Londrea J. Garrett , Igor Jovanovic , George C.-Y. Chan
We present a detailed investigation of the temporal evolution of line and continuum emissions in laser-induced breakdown spectroscopy (LIBS) of gaseous uranium hexafluoride (UF6), focusing on the spectral region near 646 nm. Spectral emission features, signal-to-background ratios (SBRs) of selected uranium lines, and spectral linewidths were examined under varying UF6 pressures (15–60 Torr) and laser pulse energies (10–60 mJ). Higher pressures and pulse energies enhanced continuum emission and reduced SBRs but did not cause significant spectral congestion. Additional studies with the use of different laser systems, including nanosecond-pulsed Nd:YAG lasers (at fundamental and various harmonics) and a femtosecond-pulsed Ti:sapphire laser, revealed long-lived plasma continua in all cases. This persistent continuum is attributed to a pseudo-continuum from overlapping molecular emissions, as its intensity scales linearly with electron number density, deviating from the expected quadratic dependence of classical ion–electron interactions for free-free and free-bound continuum emission. Based on plasma persistence time, SBR, U II/U I intensity ratios, and electronic excitation temperature, no fundamental advantage was found for femtosecond-pulsed lasers over conventional nanosecond-pulsed ones for UF6 enrichment assay with direct LIBS measurement.
{"title":"Spectral emission characteristics near 646 nm and plasma properties of laser-induced plasma of gaseous uranium hexafluoride","authors":"Londrea J. Garrett , Igor Jovanovic , George C.-Y. Chan","doi":"10.1016/j.sab.2025.107357","DOIUrl":"10.1016/j.sab.2025.107357","url":null,"abstract":"<div><div>We present a detailed investigation of the temporal evolution of line and continuum emissions in laser-induced breakdown spectroscopy (LIBS) of gaseous uranium hexafluoride (UF<sub>6</sub>), focusing on the spectral region near 646 nm. Spectral emission features, signal-to-background ratios (SBRs) of selected uranium lines, and spectral linewidths were examined under varying UF<sub>6</sub> pressures (15–60 Torr) and laser pulse energies (10–60 mJ). Higher pressures and pulse energies enhanced continuum emission and reduced SBRs but did not cause significant spectral congestion. Additional studies with the use of different laser systems, including nanosecond-pulsed Nd:YAG lasers (at fundamental and various harmonics) and a femtosecond-pulsed Ti:sapphire laser, revealed long-lived plasma continua in all cases. This persistent continuum is attributed to a pseudo-continuum from overlapping molecular emissions, as its intensity scales linearly with electron number density, deviating from the expected quadratic dependence of classical ion–electron interactions for free-free and free-bound continuum emission. Based on plasma persistence time, SBR, U II/U I intensity ratios, and electronic excitation temperature, no fundamental advantage was found for femtosecond-pulsed lasers over conventional nanosecond-pulsed ones for UF<sub>6</sub> enrichment assay with direct LIBS measurement.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107357"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814370","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 : 2025-12-24DOI: 10.1016/j.sab.2025.107312
Rebeca Pérez-Ramírez, Raquel Sánchez-Romero, Soledad Prats-Moya, Ana Beltrán-Sanahuja, José-Luis Todolí-Torró
This study presents a comparative evaluation of the high-temperature torch-integrated sample introduction system (hTISIS) and a conventional Scott double-pass spray chamber for arsenic speciation analysis by high-performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry (HPLC-ICP-MS/MS). Despite operating at low sample flow rates (c.a., 45 μL min−1) compared to the conventional system (0.5 mL min−1), the hTISIS set at 150 °C significantly enhanced sensitivity and led to five times lower limits of detection (LOD) and quantification (LOQ). Additionally, the single injection calibration approach (SICA) was implemented as an alternative quantification strategy. Unlike conventional multi-point calibration, the SICA constructs a calibration curve from the injection of a single standard, significantly shortening the calibration time by a factor of four and minimizing reagent and mobile phase consumption as well as the residue generation. The method was validated using two certified reference materials (Frozen Human Urine SRM 2669 and Apple Juice SRM 3035), achieving excellent accuracy with recoveries ranging from 92 to 110 %, and good precision (RSD <10 %). Chromatographic separation was performed using a PRP-X 100 anion-exchange column (5 μm, 150 × 2.1 mm) under gradient elution with 60 mmol L−1 ammonium bicarbonate (pH 8.7) and 5 % methanol, enabling baseline separation of arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMAA), methylarsonic acid (MMAA), and arsenobetaine (AsB) within 12 min. The hTISIS-HPLC-ICP-MS/MS assembly was successfully applied to the determination of arsenic species in commercial juice samples, demonstrating its suitability for food safety monitoring. While inorganic arsenic was found in the tested samples at concentrations (in μg kg−1) ranging from 10.4 ± 0.2 to 31 ± 2, DMAA and MMAA were only found at the 2–3 μg kg−1 level in two samples (mixed fruit and apple juice, respectively). Meanwhile, the conventional sample introduction system was not able to provide LOQs low enough to perform this kind of determinations.
本研究比较了高温火炬集成进样系统（hTISIS）和传统Scott双通道喷雾室用于高效液相色谱-电感耦合等离子体串联质谱（HPLC-ICP-MS/MS）的砷形态分析。尽管与传统系统（0.5 mL min - 1）相比，hTISIS在低样品流速（约45 μL min - 1）下工作，但在150°C下设置的hTISIS显着提高了灵敏度，并使检测下限（LOD）和定量下限（LOQ）降低了5倍。此外，采用单注射剂校准方法（SICA）作为替代的定量策略。与传统的多点校准不同，SICA从单个标准品的进样构建校准曲线，将校准时间大大缩短了四倍，并最大限度地减少了试剂和流动相的消耗以及残留物的产生。采用冷冻人尿SRM 2669和苹果汁SRM 3035两种标准物质对方法进行验证，结果表明该方法具有良好的准确度，加样回收率为92% ~ 110%，精密度为10%。色谱分离采用PRP-X 100阴离子交换柱（5 μm, 150 × 2.1 mm），以60 mmol L−1碳酸氢铵（pH 8.7）和5%甲醇梯度洗脱，使亚砷酸盐（As(III)）、砷酸盐（As(V)）、二甲基胂酸（DMAA）、甲基胂酸（MMAA）和亚砷醇碱（AsB）在12 min内基线分离。hTISIS-HPLC-ICP-MS/MS组合成功应用于商业果汁样品中砷的种类测定，证明了其在食品安全监测中的适用性。测试样品中无机砷的浓度（单位为μg kg - 1）范围为10.4±0.2至31±2，而DMAA和MMAA仅在两个样品（分别为混合水果和苹果汁）中检测到2 - 3 μg kg - 1。同时，传统的样品导入系统无法提供足够低的loq来进行这种测定。
{"title":"Combination of a high-temperature torch-integrated sample introduction system with the single injection calibration approach for arsenic speciation by HPLC-ICP-MS/MS","authors":"Rebeca Pérez-Ramírez, Raquel Sánchez-Romero, Soledad Prats-Moya, Ana Beltrán-Sanahuja, José-Luis Todolí-Torró","doi":"10.1016/j.sab.2025.107312","DOIUrl":"10.1016/j.sab.2025.107312","url":null,"abstract":"<div><div>This study presents a comparative evaluation of the high-temperature torch-integrated sample introduction system (hTISIS) and a conventional Scott double-pass spray chamber for arsenic speciation analysis by high-performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry (HPLC-ICP-MS/MS). Despite operating at low sample flow rates (<em>c.a.</em>, 45 μL min<sup>−1</sup>) compared to the conventional system (0.5 mL min<sup>−1</sup>), the hTISIS set at 150 °C significantly enhanced sensitivity and led to five times lower limits of detection (LOD) and quantification (LOQ). Additionally, the single injection calibration approach (SICA) was implemented as an alternative quantification strategy. Unlike conventional multi-point calibration, the SICA constructs a calibration curve from the injection of a single standard, significantly shortening the calibration time by a factor of four and minimizing reagent and mobile phase consumption as well as the residue generation. The method was validated using two certified reference materials (Frozen Human Urine SRM 2669 and Apple Juice SRM 3035), achieving excellent accuracy with recoveries ranging from 92 to 110 %, and good precision (RSD <10 %). Chromatographic separation was performed using a PRP-X 100 anion-exchange column (5 μm, 150 × 2.1 mm) under gradient elution with 60 mmol L<sup>−1</sup> ammonium bicarbonate (pH 8.7) and 5 % methanol, enabling baseline separation of arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMAA), methylarsonic acid (MMAA), and arsenobetaine (AsB) within 12 min. The hTISIS-HPLC-ICP-MS/MS assembly was successfully applied to the determination of arsenic species in commercial juice samples, demonstrating its suitability for food safety monitoring. While inorganic arsenic was found in the tested samples at concentrations (in μg kg<sup>−1</sup>) ranging from 10.4 ± 0.2 to 31 ± 2, DMAA and MMAA were only found at the 2–3 μg kg<sup>−1</sup> level in two samples (mixed fruit and apple juice, respectively). Meanwhile, the conventional sample introduction system was not able to provide LOQs low enough to perform this kind of determinations.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107312"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814364","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 : 2025-12-24DOI: 10.1016/j.sab.2025.107351
Rebeca Pérez-Ramírez, Raquel Sánchez-Romero, José Luis Todolí-Torró
Hydride generation (HG) remains a powerful sample introduction strategy for the determination of some elements by inductively coupled plasma mass spectrometry (ICP-MS). In this study, two HG-based configurations were systematically evaluated, including a conventional HG system with external gas-liquid separation and a structurally modified high-temperature torch-integrated sample introduction system (hTISIS). The hTISIS was equipped with an auxiliary inlet, i.e., drain tube, for the introduction of NaBH4 and HCl, allowing gas-liquid reaction and phase separation to occur directly within the thermostated spray chamber. This latter setup, HG-hTISIS, was employed under three different modes: sample introduction through both the nebulizer and the drain tube (mode 1); sample introduction only through nebulization (mode 2); and sample introduction only through the drain tube (mode 3). In all three instances, hydride-forming reagents were continuously delivered by means of the drain tube.
The operability of all configurations was assessed for five hydride-forming elements (As, Se, Sb, Sn, Bi), while quantitative performance was ultimately established using the optimized in situ HG-hTISIS configuration operated at 200 °C. Non-hydride-forming elements including Li, Al, Mn, Ti, Co, V, Cr, Ni, Cu, Zn, Rb, Sr, Ag, Ba, Cd, Tl, and Pb were also determined under this configuration, with an efficient aerosol transport enabled by the thermal chamber. A Box-Behnken design was employed to optimize the concentrations of NaOH, NaBH4, and HCl, ensuring robust hydride formation and minimal matrix effects across a wide range of conditions.
Analytical performance was evaluated in terms of sensitivity, precision, and limits of detection (LODs). Signal enhancement factors ranging from 13 to 150 were achieved for hydride-forming elements, with sub-μg L−1 detection limits and a sample uptake of only 30 μL min−1, in contrast to 0.5 mL min−1 in the conventional HG system. Moreover, foam formation was significantly mitigated in biological matrices, allowing direct analysis after sample dilution. Accuracy was confirmed through the analysis of certified reference materials of environmental and clinical origin, showing good agreement with the certified values. These results highlighted the analytical potential of the hydride generation HG-hTISIS configuration as a sensitive, low-consumption, and multielement-compatible alternative for the analysis of complex matrices by ICP-MS.
在电感耦合等离子体质谱（ICP-MS）测定某些元素时，氢化物生成（HG）仍然是一种强有力的进样策略。在这项研究中，系统地评估了两种基于HG的配置，包括具有外部气液分离的传统HG系统和结构改进的高温火炬集成样品导入系统（hTISIS）。hTISIS配有辅助入口，即放水管，用于引入NaBH4和HCl，使气液反应和相分离直接在恒温喷雾室内进行。后一种装置HG-hTISIS在三种不同的模式下使用：通过雾化器和引流管引入样品（模式1）；样品只通过雾化引入（模式2）；而样品导入只能通过引流管（模式3）。在所有三种情况下，氢化物形成试剂都是通过引流管连续输送的。对5种氢化物形成元素（As, Se, Sb, Sn, Bi）进行了所有构型的可操作性评估，并最终使用优化的原位HG-hTISIS构型在200°C下建立了定量性能。非氢化物形成元素包括Li， Al, Mn, Ti, Co， V, Cr, Ni, Cu, Zn, Rb, Sr, Ag, Ba, Cd， Tl和Pb也在这种配置下进行了测定，通过热室实现了有效的气溶胶输送。采用Box-Behnken设计来优化NaOH、NaBH4和HCl的浓度，确保在广泛的条件下氢化物形成和最小的基质效应。根据灵敏度、精密度和检出限（lod）对分析性能进行评价。形成氢化物的信号增强因子为13 ~ 150，检测限为亚μL - 1，样品吸收量仅为30 μL min - 1，而传统HG系统的吸收量为0.5 mL min - 1。此外，泡沫形成在生物基质显著减轻，允许样品稀释后直接分析。通过对环境和临床来源的认证标准物质进行分析，证实了准确性，与认证值吻合良好。这些结果突出了氢化物生成HG-hTISIS配置的分析潜力，作为ICP-MS分析复杂基质的敏感，低消耗和多元素兼容的替代方案。
{"title":"In situ hydride generation for multielement analysis in complex matrices through ICP-MS with a high-temperature sample introduction system","authors":"Rebeca Pérez-Ramírez, Raquel Sánchez-Romero, José Luis Todolí-Torró","doi":"10.1016/j.sab.2025.107351","DOIUrl":"10.1016/j.sab.2025.107351","url":null,"abstract":"<div><div>Hydride generation (HG) remains a powerful sample introduction strategy for the determination of some elements by inductively coupled plasma mass spectrometry (ICP-MS). In this study, two HG-based configurations were systematically evaluated, including a conventional HG system with external gas-liquid separation and a structurally modified high-temperature torch-integrated sample introduction system (hTISIS). The hTISIS was equipped with an auxiliary inlet, i.e., drain tube, for the introduction of NaBH<sub>4</sub> and HCl, allowing gas-liquid reaction and phase separation to occur directly within the thermostated spray chamber. This latter setup, HG-hTISIS, was employed under three different modes: sample introduction through both the nebulizer and the drain tube (mode 1); sample introduction only through nebulization (mode 2); and sample introduction only through the drain tube (mode 3). In all three instances, hydride-forming reagents were continuously delivered by means of the drain tube.</div><div>The operability of all configurations was assessed for five hydride-forming elements (As, Se, Sb, Sn, Bi), while quantitative performance was ultimately established using the optimized in situ HG-hTISIS configuration operated at 200 °C. Non-hydride-forming elements including Li, Al, Mn, Ti, Co, V, Cr, Ni, Cu, Zn, Rb, Sr, Ag, Ba, Cd, Tl, and Pb were also determined under this configuration, with an efficient aerosol transport enabled by the thermal chamber. A Box-Behnken design was employed to optimize the concentrations of NaOH, NaBH<sub>4</sub>, and HCl, ensuring robust hydride formation and minimal matrix effects across a wide range of conditions.</div><div>Analytical performance was evaluated in terms of sensitivity, precision, and limits of detection (LODs). Signal enhancement factors ranging from 13 to 150 were achieved for hydride-forming elements, with sub-μg L<sup>−1</sup> detection limits and a sample uptake of only 30 μL min<sup>−1</sup>, in contrast to 0.5 mL min<sup>−1</sup> in the conventional HG system. Moreover, foam formation was significantly mitigated in biological matrices, allowing direct analysis after sample dilution. Accuracy was confirmed through the analysis of certified reference materials of environmental and clinical origin, showing good agreement with the certified values. These results highlighted the analytical potential of the hydride generation HG-hTISIS configuration as a sensitive, low-consumption, and multielement-compatible alternative for the analysis of complex matrices by ICP-MS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107351"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814365","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 : 2025-12-24DOI: 10.1016/j.sab.2025.107396
Jonathan Merten , Mary Foster , Shealyn Chestnut , Kyle C. Hartig
The extent and dynamics of laser ablation are typically studied using crater imaging or by invoking the relationship between atomic emission and the mass removed. The former is a static view of a dynamic process and requires the accumulation of multiple shots in one location. The latter is complex and not absolute without calibration of the optical system with a standard of spectral radiance. We measure the mass of the atomized plume by laser atomic-absorption spectroscopy at 2 μs without external mass calibration; mass uncertainty in laser-ablation atomic absorption spectroscopy (LA-AAS) results from uncertainties in line-area fitting, tabulated oscillator strengths, and partition functions as well as a < 10 % underrepresentation of the mass due to treating the plasma as a single thermodynamic equilibrium. The LA-AAS-measured mass reflects the atoms in the probed charge states and does not include condensed matter or molecular species. The ablation efficiency under 300 mbar of helium varies significantly between the two focusing conditions used. A comparison of crater-derived masses and LA-AAS masses suggests that more defocused ablation may result in significant redeposition of material in the crater, distorting the conclusions from drilling studies and crater imaging. More focused ablation conditions result in crater-derived masses that exceed those measured with LA-AAS and suggest melt expulsion or phase explosion.
{"title":"Comparison of atomized mass and crater volume in laser ablation","authors":"Jonathan Merten , Mary Foster , Shealyn Chestnut , Kyle C. Hartig","doi":"10.1016/j.sab.2025.107396","DOIUrl":"10.1016/j.sab.2025.107396","url":null,"abstract":"<div><div>The extent and dynamics of laser ablation are typically studied using crater imaging or by invoking the relationship between atomic emission and the mass removed. The former is a static view of a dynamic process and requires the accumulation of multiple shots in one location. The latter is complex and not absolute without calibration of the optical system with a standard of spectral radiance. We measure the mass of the atomized plume by laser atomic-absorption spectroscopy at 2 μs without external mass calibration; mass uncertainty in laser-ablation atomic absorption spectroscopy (LA-AAS) results from uncertainties in line-area fitting, tabulated oscillator strengths, and partition functions as well as a < 10 % underrepresentation of the mass due to treating the plasma as a single thermodynamic equilibrium. The LA-AAS-measured mass reflects the atoms in the probed charge states and does not include condensed matter or molecular species. The ablation efficiency under 300 mbar of helium varies significantly between the two focusing conditions used. A comparison of crater-derived masses and LA-AAS masses suggests that more defocused ablation may result in significant redeposition of material in the crater, distorting the conclusions from drilling studies and crater imaging. More focused ablation conditions result in crater-derived masses that exceed those measured with LA-AAS and suggest melt expulsion or phase explosion.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107396"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814371","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 : 2025-12-24DOI: 10.1016/j.sab.2025.107311
Jordan L. Tanen, Kaveh Jorabchi
Fluorine detection has been a challenge in elemental mass spectrometry because of inefficient ion generation. Polyatomic analytical ion formation has emerged as a promising strategy to address this limitation. Here, we compare several post-plasma ion-neutral reactions that leverage affinity between scandium and F atoms to form analytical ions. A nitrogen microwave-sustained inductively-coupled atmospheric-pressure plasma (MICAP) is utilized to decompose fluorochemicals. The plasma products are sampled into an interface designed to minimize their adsorption to the surfaces, and are ionized in two main ways: 1) by scandium-containing ions generated using nano-electrospray ionization (nESI); 2) by addition of scandium to the plasma coupled with a post-MICAP corona discharge. Both avenues are also evaluated in positive- and negative-ion modes, producing ions such as ScFNO3(H2O)n+ and ScF(NO3)3−. In positive-ion mode, both approaches show similar fundamental characteristics, suggesting HF ionization as the main signal generation pathway. However, in negative-ion mode, nESI shows significantly lower ionization efficiency compared to that of the post-plasma corona discharge approach. The better ionization efficiency by negative-mode corona discharge ionization is attributed to production of more effective reagent ions for HF ionization, and possibility of ionizing Sc- and F-containing neutral plasma products. Importantly, the isobaric interferences are significantly decreased in negative-ion mode, improving analytical performance. Further, negative-mode ionization offers better tolerance to sodium matrix compared to that of positive-mode ionization, attributed to decreased clustering tendencies of negative ions with plasma-produced NaNO3 upon sodium introduction. These studies provide critical insights to further improve post-plasma chemical ionization for F detection.
{"title":"Comparison of scandium-based post-plasma chemical ionization approaches for elemental fluorine detection by nitrogen microwave-sustained inductively-coupled atmospheric-pressure plasma","authors":"Jordan L. Tanen, Kaveh Jorabchi","doi":"10.1016/j.sab.2025.107311","DOIUrl":"10.1016/j.sab.2025.107311","url":null,"abstract":"<div><div>Fluorine detection has been a challenge in elemental mass spectrometry because of inefficient ion generation. Polyatomic analytical ion formation has emerged as a promising strategy to address this limitation. Here, we compare several post-plasma ion-neutral reactions that leverage affinity between scandium and F atoms to form analytical ions. A nitrogen microwave-sustained inductively-coupled atmospheric-pressure plasma (MICAP) is utilized to decompose fluorochemicals. The plasma products are sampled into an interface designed to minimize their adsorption to the surfaces, and are ionized in two main ways: 1) by scandium-containing ions generated using nano-electrospray ionization (nESI); 2) by addition of scandium to the plasma coupled with a post-MICAP corona discharge. Both avenues are also evaluated in positive- and negative-ion modes, producing ions such as ScFNO<sub>3</sub>(H<sub>2</sub>O)<sub>n</sub><sup>+</sup> and ScF(NO<sub>3</sub>)<sub>3</sub><sup>−</sup>. In positive-ion mode, both approaches show similar fundamental characteristics, suggesting HF ionization as the main signal generation pathway. However, in negative-ion mode, nESI shows significantly lower ionization efficiency compared to that of the post-plasma corona discharge approach. The better ionization efficiency by negative-mode corona discharge ionization is attributed to production of more effective reagent ions for HF ionization, and possibility of ionizing Sc- and F-containing neutral plasma products. Importantly, the isobaric interferences are significantly decreased in negative-ion mode, improving analytical performance. Further, negative-mode ionization offers better tolerance to sodium matrix compared to that of positive-mode ionization, attributed to decreased clustering tendencies of negative ions with plasma-produced NaNO<sub>3</sub> upon sodium introduction. These studies provide critical insights to further improve post-plasma chemical ionization for F detection.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107311"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814270","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 : 2025-12-24DOI: 10.1016/j.sab.2025.107384
Rinus Dejonghe , Ana Lores-Padin , Eduardo Bolea-Fernandez , Thibaut Van Acker , Olivier De Wever , Frank Vanhaecke
The aim of this study was to evaluate the capabilities and limitations of single-cell elemental analysis of tandem and time-of-flight ICP-mass spectrometry (SC-ICP-MS/MS and SC-ICP-ToF-MS). As partial detection of elemental distributions remains underexplored in the context of single-cell analysis, event detection, data completeness, and the reliability of derived quantitative results were investigated. The effects of detection thresholds, instrumentation type, and transient signal characteristics on the integrity of single-cell datasets and their interpretation were addressed. Red blood cells (RBCs) and peripheral blood mononuclear cells (PBMCs) were isolated, fixed with glutaraldehyde, and analyzed using both ICP-MS/MS and ICP-ToF-MS, while average contents (fg per cell) were additionally determined by bulk analysis. One key finding was that although ICP-MS/MS offers higher sensitivity, it is incompatible with multi-elemental profiling, while the sequential data acquisition for different target elements leads to inconsistent cell counts (observed cell events) during consecutive runs. In contrast, ICP-ToF-MS provides (quasi-)simultaneous detection, allowing comprehensive and consistent characterization when using an endogenous (e.g., Fe in RBCs) or exogenous (e.g., Ir from a DNA intercalator in PBMCs) cell marker. The use of such a cell marker reveals how many cells remain undetected for each element under real experimental conditions. Second, by varying signal thresholds during data processing, the influence on (partially) detected mass distributions and the impact on mean signal intensities were evaluated. This confirmed that when detection thresholds exclude low-intensity events, the resulting distributions are biased. This study underscores the need for improved instrumental sensitivity for biologically relevant low-mass elements, especially for ToF-based ICP-mass spectrometers, as well as for careful interpretation of (partially) detected datasets to avoid misleading conclusions.
{"title":"From pitfalls to progress in quantitative single-cell elemental analysis by time-of-flight ICP-mass spectrometry","authors":"Rinus Dejonghe , Ana Lores-Padin , Eduardo Bolea-Fernandez , Thibaut Van Acker , Olivier De Wever , Frank Vanhaecke","doi":"10.1016/j.sab.2025.107384","DOIUrl":"10.1016/j.sab.2025.107384","url":null,"abstract":"<div><div>The aim of this study was to evaluate the capabilities and limitations of single-cell elemental analysis of tandem and time-of-flight ICP-mass spectrometry (SC-ICP-MS/MS and SC-ICP-ToF-MS). As partial detection of elemental distributions remains underexplored in the context of single-cell analysis, event detection, data completeness, and the reliability of derived quantitative results were investigated. The effects of detection thresholds, instrumentation type, and transient signal characteristics on the integrity of single-cell datasets and their interpretation were addressed. Red blood cells (RBCs) and peripheral blood mononuclear cells (PBMCs) were isolated, fixed with glutaraldehyde, and analyzed using both ICP-MS/MS and ICP-ToF-MS, while average contents (fg per cell) were additionally determined by bulk analysis. One key finding was that although ICP-MS/MS offers higher sensitivity, it is incompatible with multi-elemental profiling, while the sequential data acquisition for different target elements leads to inconsistent cell counts (observed cell events) during consecutive runs. In contrast, ICP-ToF-MS provides (quasi-)simultaneous detection, allowing comprehensive and consistent characterization when using an endogenous (<em>e.g.</em>, Fe in RBCs) or exogenous (<em>e.g.</em>, Ir from a DNA intercalator in PBMCs) cell marker. The use of such a cell marker reveals how many cells remain undetected for each element under real experimental conditions. Second, by varying signal thresholds during data processing, the influence on (partially) detected mass distributions and the impact on mean signal intensities were evaluated. This confirmed that when detection thresholds exclude low-intensity events, the resulting distributions are biased. This study underscores the need for improved instrumental sensitivity for biologically relevant low-mass elements, especially for ToF-based ICP-mass spectrometers, as well as for careful interpretation of (partially) detected datasets to avoid misleading conclusions.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107384"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814276","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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