Pub Date : 2025-12-24DOI: 10.1016/j.sab.2025.107308
Michael G.A. Trolio, Diane Beauchemin
A universal and cost-effective method utilizing low sample uptake rate (50 μL min−1) combined with a mixed-gas plasma containing 1.1 % nitrogen is demonstrated to reduce oxide, carbon, and argide interferences while mitigating signal suppression from complex matrices. Low sample uptake rate also reduced nitrogen-based interferences in an argon plasma. On average, oxide interferences (ScO/Sc, YO/Y, ZrO/Zr, BaO/Ba) decreased by 94.0 % when comparing an argon plasma with 1 mL min−1 sample uptake rate to 50 μL min−1 in a mixed-gas plasma. Carbon-based, nitrogen-based and argide interferences decreased by 50.6 % to 95.5 % depending on plasma condition, sample uptake rate, and interference type. Furthermore, matrix-based signal suppression arising from 100 mg L−1 Na, Rb or Cs on 50 μg L−1 Li, Mg, Cr, Mn, Co, Sr, Y, and Pb were almost fully mitigated under both plasma conditions at low sample uptake rate, with an increase in matrix effect mitigation observed in the mixed-gas plasma. By minimizing sample waste and wear on costly instrument components, the enclosed method offers a greener solution for analytical laboratories, decreasing operational costs and increasing sample throughput without introducing significant error or uncertainty. Ultimately, this work can be universally implemented, without the need for costly instrument modifications or consideration for instrument make or model.
利用低样品吸收率(50 μL min - 1)与含有1.1%氮的混合气体等离子体相结合,证明了一种通用且具有成本效益的方法可以减少氧化物,碳和氩气干扰,同时减轻复杂基质的信号抑制。低样品吸收率也减少了氩等离子体中的氮基干扰。当样品吸收率为1 mL min - 1的氩气等离子体与样品吸收率为50 μL min - 1的混合气体等离子体相比,氧化物干扰(ScO/Sc、YO/Y、ZrO/Zr、BaO/Ba)平均降低了94.0%。碳基、氮基和氩气干扰减少了50.6%至95.5%,具体取决于等离子体条件、样品摄取率和干扰类型。此外,在低样品吸收率的两种等离子体条件下,100 mg L−1 Na、Rb或Cs对50 μg L−1 Li、mg、Cr、Mn、Co、Sr、Y和Pb产生的基于基质的信号抑制几乎完全被缓解,并且在混合气体等离子体中观察到基质效应的缓解增加。通过最大限度地减少样品浪费和昂贵仪器组件的磨损,封闭式方法为分析实验室提供了更环保的解决方案,降低了操作成本,提高了样品吞吐量,而不会引入显着的误差或不确定性。最终,这项工作可以普遍实施,而不需要昂贵的仪器修改或考虑仪器制造或型号。
{"title":"A universal and cost-effective method for the mitigation of interferences in inductively coupled plasma mass spectrometry","authors":"Michael G.A. Trolio, Diane Beauchemin","doi":"10.1016/j.sab.2025.107308","DOIUrl":"10.1016/j.sab.2025.107308","url":null,"abstract":"<div><div>A universal and cost-effective method utilizing low sample uptake rate (50 μL min<sup>−1</sup>) combined with a mixed-gas plasma containing 1.1 % nitrogen is demonstrated to reduce oxide, carbon, and argide interferences while mitigating signal suppression from complex matrices. Low sample uptake rate also reduced nitrogen-based interferences in an argon plasma. On average, oxide interferences (ScO/Sc, YO/Y, ZrO/Zr, BaO/Ba) decreased by 94.0 % when comparing an argon plasma with 1 mL min<sup>−1</sup> sample uptake rate to 50 μL min<sup>−1</sup> in a mixed-gas plasma. Carbon-based, nitrogen-based and argide interferences decreased by 50.6 % to 95.5 % depending on plasma condition, sample uptake rate, and interference type. Furthermore, matrix-based signal suppression arising from 100 mg L<sup>−1</sup> Na, Rb or Cs on 50 μg L<sup>−1</sup> Li, Mg, Cr, Mn, Co, Sr, Y, and Pb were almost fully mitigated under both plasma conditions at low sample uptake rate, with an increase in matrix effect mitigation observed in the mixed-gas plasma. By minimizing sample waste and wear on costly instrument components, the enclosed method offers a greener solution for analytical laboratories, decreasing operational costs and increasing sample throughput without introducing significant error or uncertainty. Ultimately, this work can be universally implemented, without the need for costly instrument modifications or consideration for instrument make or model.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107308"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814362","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.2025.107379
Aline Pereira de Oliveira , Ana Lores-Padín , Thibaut Van Acker , Iker Basabe-Mendizabal , Helton Pereira Nogueira , Juliana Naozuka , Cassiana Seimi Nomura , Frank Vanhaecke
The increasing use of nanomaterials has raised concerns regarding their environmental fate and impact on food safety. Nanoparticles (NPs) can be taken up by plants, undergo biotransformation, and accumulate in edible parts. While single-particle inductively coupled plasma-mass spectrometry (spICP-MS) allows characterization of NPs in suspension, it requires their extraction from biological tissues, erasing spatial information and potentially affecting particle integrity. In contrast, laser ablation–single-particle ICP–time of flight MS (LA-spICP-ToFMS) enables spatially resolved analysis via direct solid sampling, revealing the distribution of NPs and ionic species in plant tissues. A calibration approach based on gelatin microdroplets was developed for quantitative mapping of AuNPs and essential elements in plant tissues. Microdroplets (0.015–0.100 mg) containing 30, 50, or 100 nm AuNPs (8 × 104 particles mg−1) and suitable amounts of Cu, Fe, and Mn were manually deposited on microscope slides and ablated using an ArF*excimer-based LA system equipped with a low-dispersion tube-type cell. Mapping was performed with a 20 × 20 μm spot at low fluence (0.25 J cm−2) to preserve NP integrity. The transport efficiency for AuNPs ranged from 95 to 105 % for all sizes (30–100 nm). As proof of concept, cotyledon and stem cross-sections of Phaseolus vulgaris seedlings cultivated with ionic Au or 30 ± 3 nm AuNPs (both at 1 mg L−1 Au), or without added Au, were analyzed. The method revealed AuNPs spatial distribution, particle concentration and size distribution, and effects on essential elements, proving suitable for assessing uptake, translocation, and interactions of AuNPs in plant systems.
{"title":"Quantitative mapping of gold nanoparticles and essential elements in plant tissue using laser ablation–single-particle inductively coupled plasma–time of flight mass spectrometry","authors":"Aline Pereira de Oliveira , Ana Lores-Padín , Thibaut Van Acker , Iker Basabe-Mendizabal , Helton Pereira Nogueira , Juliana Naozuka , Cassiana Seimi Nomura , Frank Vanhaecke","doi":"10.1016/j.sab.2025.107379","DOIUrl":"10.1016/j.sab.2025.107379","url":null,"abstract":"<div><div>The increasing use of nanomaterials has raised concerns regarding their environmental fate and impact on food safety. Nanoparticles (NPs) can be taken up by plants, undergo biotransformation, and accumulate in edible parts. While single-particle inductively coupled plasma-mass spectrometry (spICP-MS) allows characterization of NPs in suspension, it requires their extraction from biological tissues, erasing spatial information and potentially affecting particle integrity. In contrast, laser ablation–single-particle ICP–time of flight MS (LA-spICP-ToFMS) enables spatially resolved analysis via direct solid sampling, revealing the distribution of NPs <em>and</em> ionic species in plant tissues. A calibration approach based on gelatin microdroplets was developed for quantitative mapping of AuNPs and essential elements in plant tissues. Microdroplets (0.015–0.100 mg) containing 30, 50, or 100 nm AuNPs (8 × 10<sup>4</sup> particles mg<sup>−1</sup>) and suitable amounts of Cu, Fe, and Mn were manually deposited on microscope slides and ablated using an ArF*excimer-based LA system equipped with a low-dispersion tube-type cell. Mapping was performed with a 20 × 20 μm spot at low fluence (0.25 J cm<sup>−2</sup>) to preserve NP integrity. The transport efficiency for AuNPs ranged from 95 to 105 % for all sizes (30–100 nm). As proof of concept, cotyledon and stem cross-sections of <em>Phaseolus vulgaris</em> seedlings cultivated with ionic Au or 30 ± 3 nm AuNPs (both at 1 mg L<sup>−1</sup> Au), or without added Au, were analyzed. The method revealed AuNPs spatial distribution, particle concentration and size distribution, and effects on essential elements, proving suitable for assessing uptake, translocation, and interactions of AuNPs in plant systems.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107379"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814363","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.2025.107423
Patrick J. Gray
{"title":"A tribute to mentor and advisor Dr. John Olesik on his 70th birthday","authors":"Patrick J. Gray","doi":"10.1016/j.sab.2025.107423","DOIUrl":"10.1016/j.sab.2025.107423","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107423"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814275","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.2025.107446
Letícia C. Brudi, Eliana T.F. Larruscain, Andressa D.W.V. Martinez, Gustavo R. Bitencourt, Paola A. Mello, Fabio A. Duarte
The purpose of this study was to develop a method coupling chemical vapor generation (CVG) and microwave-induced plasma optical emission spectrometry (MIP OES) for the determination of As, Bi, Cd, Ge, Hg, Sb and Sn in environmental matrices, such as coal, marine, and lake sediment. The main parameters for the development of CVG-MIP OES method were the concentration of NaBH4 (0.1 to 2 % m/v) and HCl (1 to 7 mol L−1) solutions, the type (thiourea, L-cysteine, potassium iodide and hydroxylamine hydrochloride) and concentration (0.1 to 2 % m/v) of pre-reducing agents solutions, the operational conditions for MIP OES instrument, the interferences caused by transition metals (in the range of 25 to 1000 μg L−1), and the concentration of HNO3 (5 to 40 %) in the samples. The proposed method allows for achieving limit of detection (LOD) values of 199, 45.4, 112, 75.8, 89.7, 61.9, and 79.4 ng g−1 for As, Bi, Cd, Ge, Hg, Sb, and Sn, respectively. The accuracy was evaluated by the analysis of three certified reference materials: coal (NIST 1632c), marine sediment (PACS-2) and lake sediment (SUD-1), with agreement ranging from 92 to 111 %. Thus, the CVG-MIP OES method proved to be effective for As, Bi, Cd, Ge, Hg, Sb, and Sn determination in samples with different compositions, being robust regarding HNO3 concentration and interfering metals concentration. A significant reduction in the LOD of the MIP OES technique was obtained. Finally, the proposed method is a cost-effective alternative to the traditional plasma-based techniques, due to its low long-term cost and good robustness.
本研究的目的是建立一种耦合化学蒸汽产生(CVG)和微波诱导等离子体光学发射光谱(MIP OES)的方法,用于测定煤、海洋和湖泊沉积物等环境基质中的As、Bi、Cd、Ge、Hg、Sb和Sn。CVG-MIP OES的发展方法的主要参数是NaBH4的浓度(m / v 0.1 - 2%)和盐酸(1 - 7摩尔L−1)解决方案,类型(硫脲,半胱氨酸,碘化钾和盐酸羟胺)和浓度(0.1米/ v) 2%的pre-reducing代理解决方案,MIP海洋能仪器,操作条件造成的干扰过渡金属(在25到1000μg L−1),和硝酸的浓度(5 - 40%)的样品。该方法对As、Bi、Cd、Ge、Hg、Sb和Sn的检测限(LOD)分别为199、45.4、112、75.8、89.7、61.9和79.4 ng g−1。准确度通过分析三种认证标准物质进行评估:煤(NIST 1632c),海洋沉积物(PACS-2)和湖泊沉积物(SUD-1),一致性范围为92%至111%。因此,CVG-MIP OES法对不同成分样品的As、Bi、Cd、Ge、Hg、Sb、Sn的测定是有效的,对HNO3浓度和干扰金属浓度的测定是稳健的。MIP OES技术的LOD显著降低。最后,该方法长期成本低,鲁棒性好,是传统等离子体技术的一种经济有效的替代方法。
{"title":"Fast-sequential determination of As, Bi, Cd, Ge, Hg, Sb and Sn by CVG-MIP OES using a multimode sample introduction system","authors":"Letícia C. Brudi, Eliana T.F. Larruscain, Andressa D.W.V. Martinez, Gustavo R. Bitencourt, Paola A. Mello, Fabio A. Duarte","doi":"10.1016/j.sab.2025.107446","DOIUrl":"10.1016/j.sab.2025.107446","url":null,"abstract":"<div><div>The purpose of this study was to develop a method coupling chemical vapor generation (CVG) and microwave-induced plasma optical emission spectrometry (MIP OES) for the determination of As, Bi, Cd, Ge, Hg, Sb and Sn in environmental matrices, such as coal, marine, and lake sediment. The main parameters for the development of CVG-MIP OES method were the concentration of NaBH<sub>4</sub> (0.1 to 2 % m/v) and HCl (1 to 7 mol L<sup>−1</sup>) solutions, the type (thiourea, L-cysteine, potassium iodide and hydroxylamine hydrochloride) and concentration (0.1 to 2 % m/v) of pre-reducing agents solutions, the operational conditions for MIP OES instrument, the interferences caused by transition metals (in the range of 25 to 1000 μg L<sup>−1</sup>), and the concentration of HNO<sub>3</sub> (5 to 40 %) in the samples. The proposed method allows for achieving limit of detection (LOD) values of 199, 45.4, 112, 75.8, 89.7, 61.9, and 79.4 ng g<sup>−1</sup> for As, Bi, Cd, Ge, Hg, Sb, and Sn, respectively. The accuracy was evaluated by the analysis of three certified reference materials: coal (NIST 1632c), marine sediment (PACS-2) and lake sediment (SUD-1), with agreement ranging from 92 to 111 %. Thus, the CVG-MIP OES method proved to be effective for As, Bi, Cd, Ge, Hg, Sb, and Sn determination in samples with different compositions, being robust regarding HNO<sub>3</sub> concentration and interfering metals concentration. A significant reduction in the LOD of the MIP OES technique was obtained. Finally, the proposed method is a cost-effective alternative to the traditional plasma-based techniques, due to its low long-term cost and good robustness.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107446"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883997","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.2025.107306
Nivethika Komathinathan , Kevin Kraft , Philipp Schuetz , Florian Kehl , Davide Bleiner
In-situ resource identification on extraterrestrial bodies is pivotal for space exploration and necessitates precise material characterization techniques. This study evaluates the comparative performance of Laser-Induced Soft X-ray and Extreme Ultraviolet (XUV) Spectroscopy (LIXS) and conventional Laser-Induced Breakdown Spectroscopy (LIBS) for this purpose. LIXS, designed to operate at shorter wavelengths and to detect signals in vacuum, aims to enhance extraplanetary exploration tools along with its environmental compatibility, particularly on the lunar surface. A key hypothesis of our study is that LIXS is more repeatable and reproducible compared to LIBS, which are known limitations of LIBS. This analysis includes the evaluation of repeatability and reproducibility for three prominent emission lines from lunar analogue samples as well as for the emission of aluminum from the same samples using both detection methods. The investigation reveals that a maximum relative standard deviation (RSD) for aluminum emission intensities of 11.1 % is achieved by LIXS and of 208.2 % by LIBS at equivalent energies, signifying notably enhanced repeatability. Additionally, LIXS exhibits up to eight times better reproducibility of aluminum emission intensities in diverse experimental setting conditions compared to LIBS. Signal-to-noise ratio analysis further underscores the advantages of noise reduction by LIXS, contributing to its better performance, establishing LIXS as a superior alternative with enhanced repeatability and reproducibility for resource identification in space exploration.
{"title":"Enhanced repeatability and reproducibility in lunar analog material analysis using LIXS compared to LIBS","authors":"Nivethika Komathinathan , Kevin Kraft , Philipp Schuetz , Florian Kehl , Davide Bleiner","doi":"10.1016/j.sab.2025.107306","DOIUrl":"10.1016/j.sab.2025.107306","url":null,"abstract":"<div><div>In-situ resource identification on extraterrestrial bodies is pivotal for space exploration and necessitates precise material characterization techniques. This study evaluates the comparative performance of Laser-Induced Soft X-ray and Extreme Ultraviolet (XUV) Spectroscopy (LIXS) and conventional Laser-Induced Breakdown Spectroscopy (LIBS) for this purpose. LIXS, designed to operate at shorter wavelengths and to detect signals in vacuum, aims to enhance extraplanetary exploration tools along with its environmental compatibility, particularly on the lunar surface. A key hypothesis of our study is that LIXS is more repeatable and reproducible compared to LIBS, which are known limitations of LIBS. This analysis includes the evaluation of repeatability and reproducibility for three prominent emission lines from lunar analogue samples as well as for the emission of aluminum from the same samples using both detection methods. The investigation reveals that a maximum relative standard deviation (RSD) for aluminum emission intensities of 11.1 % is achieved by LIXS and of 208.2 % by LIBS at equivalent energies, signifying notably enhanced repeatability. Additionally, LIXS exhibits up to eight times better reproducibility of aluminum emission intensities in diverse experimental setting conditions compared to LIBS. Signal-to-noise ratio analysis further underscores the advantages of noise reduction by LIXS, contributing to its better performance, establishing LIXS as a superior alternative with enhanced repeatability and reproducibility for resource identification in space exploration.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107306"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814368","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.2025.107309
Yi You , Boyang Xue , Jens Riedel
Laser-induced breakdown spectroscopy (LIBS) offers versatile, field-deployable elemental analysis; however, compact, high-repetition-rate nanosecond laser systems typically face constraints in power consumption and size, often compromising emission intensity and thus analytical performance. We demonstrate a significant improvement in LIBS signals through the controlled introduction of common organic solvent vapors into a sheath gas, with a diode-pumped solid-state laser (1064 nm, 2–28 kHz repetition rate, 450–600-μJ pulse energy). Optical and acoustic diagnostics reveal up to ca. 40-fold enhancement of the N II emission line at 567 nm when ambient air serves as the analyte. Maximal enhancement occurs at intermediate repetition rates of ca. 15 kHz, particularly at pulse energies approaching the optical breakdown threshold; this observation suggests a viable strategy for operating LIBS at lower pulse energies and higher repetition rates. Enhancement effects scale jointly with both vapor pressure and ionization energy of the organic species, with acetone and toluene markedly outperforming methanol and isopropanol. These findings provide a rational foundation for significantly improving the analytical performance of portable LIBS instruments without exceeding platform-specific constraints.
{"title":"Enhancement of LIBS plasma in air with organic solvent vapors","authors":"Yi You , Boyang Xue , Jens Riedel","doi":"10.1016/j.sab.2025.107309","DOIUrl":"10.1016/j.sab.2025.107309","url":null,"abstract":"<div><div>Laser-induced breakdown spectroscopy (LIBS) offers versatile, field-deployable elemental analysis; however, compact, high-repetition-rate nanosecond laser systems typically face constraints in power consumption and size, often compromising emission intensity and thus analytical performance. We demonstrate a significant improvement in LIBS signals through the controlled introduction of common organic solvent vapors into a sheath gas, with a diode-pumped solid-state laser (1064 nm, 2–28 kHz repetition rate, 450–600-μJ pulse energy). Optical and acoustic diagnostics reveal up to ca. 40-fold enhancement of the N II emission line at 567 nm when ambient air serves as the analyte. Maximal enhancement occurs at intermediate repetition rates of ca. 15 kHz, particularly at pulse energies approaching the optical breakdown threshold; this observation suggests a viable strategy for operating LIBS at lower pulse energies and higher repetition rates. Enhancement effects scale jointly with both vapor pressure and ionization energy of the organic species, with acetone and toluene markedly outperforming methanol and isopropanol. These findings provide a rational foundation for significantly improving the analytical performance of portable LIBS instruments without exceeding platform-specific constraints.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107309"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814369","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.2025.107307
Isabel Abad-Alvaro, Eduardo Bolea, Francisco Laborda
Performance of single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) methods is constrained by the characteristics of the instrumentation. The commercial availability of fast data acquisition quadrupole instruments, which allow the use of dwell times in the microsecond range rather than being restricted to milliseconds, was expected to improve the performance of the technique. When data acquisition frequency is increased, individual particles are recorded as transient signals consisting of multiple-reading events instead of one-reading pulses. Since particle events must be detected above the baseline noise, the highest intensity reading of a transient signal becomes a relevant parameter whose value decreases with decreasing dwell time, as the total intensity of a particle event is independent of the number of readings per event and thus of the selected dwell time. In this work, the effect of dwell time on the attainable size detection limits has been reconsidered, achieving minimum size detection limits when dwell times in the range of 200–500 μs were used, regardless of the baseline level. At such dwell times, particle events from small nanoparticles (e.g., 2–3 times the size detection limit) were recorded within 1–2 readings despite the duration of particle events, which was modified working in both standard and gas reaction modes. Under these conditions, free and proprietary software capable of handling multiple-reading events allowed to process successfully the SP-ICP-MS data independently of the dwell time applied.
{"title":"Size detection limits in single particle inductively coupled plasma mass spectrometry: Reconsidering the selection of dwell times","authors":"Isabel Abad-Alvaro, Eduardo Bolea, Francisco Laborda","doi":"10.1016/j.sab.2025.107307","DOIUrl":"10.1016/j.sab.2025.107307","url":null,"abstract":"<div><div>Performance of single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) methods is constrained by the characteristics of the instrumentation. The commercial availability of fast data acquisition quadrupole instruments, which allow the use of dwell times in the microsecond range rather than being restricted to milliseconds, was expected to improve the performance of the technique. When data acquisition frequency is increased, individual particles are recorded as transient signals consisting of multiple-reading events instead of one-reading pulses. Since particle events must be detected above the baseline noise, the highest intensity reading of a transient signal becomes a relevant parameter whose value decreases with decreasing dwell time, as the total intensity of a particle event is independent of the number of readings per event and thus of the selected dwell time. In this work, the effect of dwell time on the attainable size detection limits has been reconsidered, achieving minimum size detection limits when dwell times in the range of 200<em>–</em>500 μs were used, regardless of the baseline level. At such dwell times, particle events from small nanoparticles (e.g., 2<em>–</em>3 times the size detection limit) were recorded within 1<em>–</em>2 readings despite the duration of particle events, which was modified working in both standard and gas reaction modes. Under these conditions, free and proprietary software capable of handling multiple-reading events allowed to process successfully the SP-ICP-MS data independently of the dwell time applied.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107307"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814361","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.2025.107339
George C.-Y. Chan , Gary M. Hieftje
A search for causes of intermittent mid-term (about two hours) instability in emission signals from an inductively coupled plasma led to adoption of a tandem spray-chamber arrangement and subsequently to use of a surfactant (Triton X-100) to mitigate the remaining and newly found instabilities. Through a series of investigations, abrupt signal excursions in the tandem setup were traced to droplet coagulation and drainage inside the glass tube that connected the two spray chambers. However, the signal shifts were not the result of sample-solution release directly but rather to the influence of the underlying factors on plasma behavior. Experiments tailored to the study included not only examination of temporal signal behavior but also collection of long-term videos and measurement of radiofrequency characteristics of the plasma. The addition of a surfactant, Triton X-100, for signal-stability improvement is applicable not only to systems that employ tandem spray chambers but also to conventional single Scott-type chamber arrangements. Further, use of the surfactant was unsuccessful in overcoming “acid effects”, either of the steady-state or transient nature, and did not alter plasma background or analyte signals significantly.
{"title":"Improved signal stability in inductively coupled plasma–atomic emission spectrometry through use of tandem spray chambers and surfactant addition","authors":"George C.-Y. Chan , Gary M. Hieftje","doi":"10.1016/j.sab.2025.107339","DOIUrl":"10.1016/j.sab.2025.107339","url":null,"abstract":"<div><div>A search for causes of intermittent mid-term (about two hours) instability in emission signals from an inductively coupled plasma led to adoption of a tandem spray-chamber arrangement and subsequently to use of a surfactant (Triton X-100) to mitigate the remaining and newly found instabilities. Through a series of investigations, abrupt signal excursions in the tandem setup were traced to droplet coagulation and drainage inside the glass tube that connected the two spray chambers. However, the signal shifts were not the result of sample-solution release directly but rather to the influence of the underlying factors on plasma behavior. Experiments tailored to the study included not only examination of temporal signal behavior but also collection of long-term videos and measurement of radiofrequency characteristics of the plasma. The addition of a surfactant, Triton X-100, for signal-stability improvement is applicable not only to systems that employ tandem spray chambers but also to conventional single Scott-type chamber arrangements. Further, use of the surfactant was unsuccessful in overcoming “acid effects”, either of the steady-state or transient nature, and did not alter plasma background or analyte signals significantly.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107339"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814367","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/S0584-8547(25)00322-2
{"title":"Outside Front Cover - Journal name, Cover image, Volume issue details, ISSN, Cover Date, Elsevier Logo and Society Logo if required","authors":"","doi":"10.1016/S0584-8547(25)00322-2","DOIUrl":"10.1016/S0584-8547(25)00322-2","url":null,"abstract":"","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"236 ","pages":"Article 107437"},"PeriodicalIF":3.8,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814334","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 : 2025-12-23DOI: 10.1016/j.sab.2025.107445
Xin Yu , Yuanfei Jiang , Hongxia Qi , Jianhui Han , Anmin Chen , Mingxing Jin
This study combines arc discharge with femtosecond laser-induced breakdown spectroscopy (fs-LIBS) to investigate the time-integrated and time-resolved spectra of aluminum atoms and AlO molecules in aluminum targets. A dried droplet method was further employed to analyze the emission spectra and calibration curves of Cu in aqueous solutions. Under arc-assisted fs-LIBS, at a laser energy of 0.5 mJ, the spectral enhancement factors reached up to 14 and 5 for Al and AlO, respectively. Vibrational temperatures of AlO were calculated as functions of laser energy and detection delay, showing consistently higher values in the presence of arc discharge. For Cu detection, the results revealed that, at a laser energy of 1 mJ, arc-assisted fs-LIBS reduced the limit of detection (LOD) of Cu (I) at 324.75 nm from 187 ng/mL to 25 ng/mL, and at 327.40 nm from 191 ng/mL to 31 ng/mL—corresponding to an improvement of ∼7 and 6-fold respectively over conventional fs-LIBS. The correlation coefficient (R2) of the calibration curve also improved, from 0.949 to 0.951 at 324.75 nm and from 0.896 to 0.957 at 327.40 nm. These results indicate that at relatively low laser energy, arc discharge-assisted fs-LIBS not only enhances the detection sensitivity of Al and AlO species, but also significantly improves the analytical performance of trace Cu in liquids, thereby expanding the applicability of femtosecond LIBS in high-sensitivity spectroscopic analysis.
{"title":"Arc discharge-assisted enhancement of femtosecond LIBS for improved sensitivity in trace Cu detection in aqueous solutions","authors":"Xin Yu , Yuanfei Jiang , Hongxia Qi , Jianhui Han , Anmin Chen , Mingxing Jin","doi":"10.1016/j.sab.2025.107445","DOIUrl":"10.1016/j.sab.2025.107445","url":null,"abstract":"<div><div>This study combines arc discharge with femtosecond laser-induced breakdown spectroscopy (fs-LIBS) to investigate the time-integrated and time-resolved spectra of aluminum atoms and AlO molecules in aluminum targets. A dried droplet method was further employed to analyze the emission spectra and calibration curves of Cu in aqueous solutions. Under arc-assisted fs-LIBS, at a laser energy of 0.5 mJ, the spectral enhancement factors reached up to 14 and 5 for Al and AlO, respectively. Vibrational temperatures of AlO were calculated as functions of laser energy and detection delay, showing consistently higher values in the presence of arc discharge. For Cu detection, the results revealed that, at a laser energy of 1 mJ, arc-assisted fs-LIBS reduced the limit of detection (LOD) of Cu (I) at 324.75 nm from 187 ng/mL to 25 ng/mL, and at 327.40 nm from 191 ng/mL to 31 ng/mL—corresponding to an improvement of ∼7 and 6-fold respectively over conventional fs-LIBS. The correlation coefficient (R<sup>2</sup>) of the calibration curve also improved, from 0.949 to 0.951 at 324.75 nm and from 0.896 to 0.957 at 327.40 nm. These results indicate that at relatively low laser energy, arc discharge-assisted fs-LIBS not only enhances the detection sensitivity of Al and AlO species, but also significantly improves the analytical performance of trace Cu in liquids, thereby expanding the applicability of femtosecond LIBS in high-sensitivity spectroscopic analysis.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107445"},"PeriodicalIF":3.8,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145840084","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}