Pub Date : 2026-03-01Epub 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":"2026-03-01","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}
Pub Date : 2026-03-01Epub 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":"2026-03-01","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 : 2026-03-01Epub Date: 2025-11-21DOI: 10.1016/j.sab.2025.107399
Asmaa M. Abozied , Abdulkader M. Elmagrabi , Zein K. Heiba , Hikari Takahara , Kouichi Tsuji , Somchai Tancharakorn , Abdallah A. Shaltout
To prevent the deterioration of natural resources and support sustainable development, the valorization and recycling of various steel slags have become increasingly important. In the present work, six different types of steel slags were collected, characterized, and analyzed: electric arc furnace (EAF) slag, ladle refining furnace slag treated with Si and Al (LRF-Si and LRFAl), steel fume dust, mill scale flakes, and refractory materials waste. High resolution wavelength dispersive X-ray fluorescence (WDXRF) spectrometry with multi-dispersive crystals was used for precise quantitative elemental analysis. X-ray diffractometry was employed to identify and quantify the crystalline phases analysis within the collected samples. The analysis revealed that the mill scale flakes and EAF slags contain high concentrations of iron oxides, at approximately ∼95 % and ∼ 40 %, respectively, making them attractive for various applications. The high concentration of calcium oxides and calcium compounds in LRF slag (∼ 50 %) makes it suitable for various applications in the cement and concrete industry. Furthermore, the steel fume dust was found to contain a remarkably high concentration of zinc oxides (ZnO) reaching to ∼40 %. The high ZnO content makes the steel fume dust a promising candidate for many applications such as zinc extraction, fertilizers productions, and cosmetics.
{"title":"Valorization of steel slags through elemental and phase characterization using X-ray spectrometries","authors":"Asmaa M. Abozied , Abdulkader M. Elmagrabi , Zein K. Heiba , Hikari Takahara , Kouichi Tsuji , Somchai Tancharakorn , Abdallah A. Shaltout","doi":"10.1016/j.sab.2025.107399","DOIUrl":"10.1016/j.sab.2025.107399","url":null,"abstract":"<div><div>To prevent the deterioration of natural resources and support sustainable development, the valorization and recycling of various steel slags have become increasingly important. In the present work, six different types of steel slags were collected, characterized, and analyzed: electric arc furnace (EAF) slag, ladle refining furnace slag treated with Si and Al (LRF-Si and LRF<img>Al), steel fume dust, mill scale flakes, and refractory materials waste. High resolution wavelength dispersive X-ray fluorescence (WDXRF) spectrometry with multi-dispersive crystals was used for precise quantitative elemental analysis. X-ray diffractometry was employed to identify and quantify the crystalline phases analysis within the collected samples. The analysis revealed that the mill scale flakes and EAF slags contain high concentrations of iron oxides, at approximately ∼95 % and ∼ 40 %, respectively, making them attractive for various applications. The high concentration of calcium oxides and calcium compounds in LRF slag (∼ 50 %) makes it suitable for various applications in the cement and concrete industry. Furthermore, the steel fume dust was found to contain a remarkably high concentration of zinc oxides (ZnO) reaching to ∼40 %. The high ZnO content makes the steel fume dust a promising candidate for many applications such as zinc extraction, fertilizers productions, and cosmetics.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107399"},"PeriodicalIF":3.8,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617381","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 : 2026-03-01Epub 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":"2026-03-01","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 : 2026-02-01Epub 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":"2026-02-01","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 : 2026-02-01Epub 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":"2026-02-01","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 : 2026-02-01Epub 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":"2026-02-01","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 : 2026-02-01Epub 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":"2026-02-01","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 : 2026-02-01Epub 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":"2026-02-01","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 : 2026-02-01Epub Date: 2025-12-24DOI: 10.1016/j.sab.2025.107424
Paul B. Farnsworth
{"title":"A tribute to John Olesik","authors":"Paul B. Farnsworth","doi":"10.1016/j.sab.2025.107424","DOIUrl":"10.1016/j.sab.2025.107424","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107424"},"PeriodicalIF":3.8,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814273","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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