Journal of Analytical Atomic Spectrometry最新文献

{"title":"<i>In situ</i> analysis of titanium isotope ratios in stardust using LA-CC-MC-ICPMS/MS.","authors":"Kathryn M M Shaw, Markus Pfeifer, Benjamin L L Coath, Jamie Lewis, Dan Bevan, Christopher D Coath, Tim Elliott","doi":"10.1039/d5ja00068h","DOIUrl":"10.1039/d5ja00068h","url":null,"abstract":"<p><p>Presolar grains are nanometre-scale dust grains that exhibit large isotope excursions that illustrate the stellar isotopic input into the Solar System. Further, it is thought that they were differentially incorporated into meteorite parent bodies and thus can be used to trace planetary genetics and construction. <i>In situ</i> mapping of the distribution of presolar grains in the matrix of primitive meteorites therefore provides a key means to achieve this goal. However, <i>in situ</i> methods complicate isotopic measurements, such as those of Ti, due to their large isobaric interferences. To enable such measurements a prototype a collision cell, multicollector inductively-coupled plasma mass spectrometer with a pre-cell mass filter (CC-MC-ICPMS/MS) was developed and called Proteus. In this study we show that, when coupled to a laser ablation system, Proteus has the capability to measure, <i>in situ</i>, large Ti isotope excursions such as those expected in presolar grains (>200‰). Within the collision cell we introduced O₂ gas and react Ti⁺ to TiO⁺ and perform the multi-collector isotope ratio measurement on the TiO⁺ species. The presence of isobaric interferences from Ca⁺, V⁺, and Cr⁺ are greatly reduced due to their lower ion reaction efficiency with O₂ gas. The measurement of TiO⁺ using the pre-cell mass filter ensures that these ions are measured in a cleared region of the mass-spectrum where a Ni⁺, Cu⁺, and Zn⁺ ions would otherwise be present as interferences. Using this technique, complex rock samples with high Ca/Ti and Cr/Ti, for example BIR-1G, give the same mass-independent isotopic Ti ratios as essentially pure Ti-minerals, <i>e.g.</i> brookite. By reducing isobaric interferences from <i>in situ</i> measurements we can detect the large isotopic excursions in presolar grains without the added impediment of non-solar interference corrections for isobaric interferences.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12097295/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144140974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Determination of the uptake of lanthanide doped-carbon dots by human cells using single cell ICP-ToF-MS†","authors":"Guillermo Redondo-Fernandez, Kharmen Billimoria, Simon Cowen, David Ojeda, Dorota Bartczak, Ana Soldado, Jose M. Costa-Fernandez and Heidi Goenaga-Infante","doi":"10.1039/D5JA00075K","DOIUrl":"https://doi.org/10.1039/D5JA00075K","url":null,"abstract":"<p >As the application of engineered nanoparticles in medical fields grows, there is a rising demand for techniques capable of determining how they interact with biological entities, including cells. Single Cell Inductively Coupled Plasma Time-of-Flight Mass Spectrometry (sc-ICP-ToF-MS) has been shown potential to assess the mass of nanoparticle tags uptaken by individual cells. However, this approach suffers from challenges related to inconsistencies in transport efficiency (TE) determination and data processing protocols, which greatly impact the quality of the data. To address these issues, a novel metrological approach for the identification of cell events and determination of their TE is presented here for the first time. It is based on using the ratio of Eu to Yb signals in a single event to distinguish cellular events from background noise when analyzing HeLa cells tagged with lanthanide-doped carbon dots (Ln-CDs). To achieve this, Ln-CDs with Eu (4.3%) and Yb (3.4%) were synthesized, characterized and cytotoxicity assays were performed to confirm their biocompatibility. HeLa cells were exposed to these multielement Ln-CDs at varying concentrations to evaluate their cellular uptake. Laser ablation (LA)-ICP-MS analysis of individual isolated cells (<em>n</em> = 1578) confirmed cell tagging efficiency of 99.87%. Using this approach and CytoNeb–CytoSpray interface, TE values between 40–50% were achieved. The results showed a dosage dependent uptake of Ln-CDs by cells, with final concentrations ranging from 6.8 to 5115 fg Ln-CDs per cell.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1403-1410"},"PeriodicalIF":3.1,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00075k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913795","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In situ Re–Os geochronology of Re-rich Palaeogene molybdenite by LA-ICP-MS/MS†","authors":"Stijn Glorie, Jay M. Thompson, Sarah E. Gilbert and A. Kate Souders","doi":"10.1039/D5JA00030K","DOIUrl":"https://doi.org/10.1039/D5JA00030K","url":null,"abstract":"<p > <em>In situ</em> Re–Os geochronology by LA-ICP-MS/MS was previously demonstrated by reacting Os with CH<small>₄</small> or N<small>₂</small>O reaction gasses. However, for both reactions, a minor proportion of the Re parent isotope also reacts, potentially leading to significant isobaric interferences of <small>¹⁸⁷</small>Re on <small>¹⁸⁷</small>Os, especially for young samples with little radiogenic in-growth. Here we present an interlaboratory comparison and compare three reaction gas mixtures (CH<small>₄</small> + H<small>₂</small> + He, N<small>₂</small>O and N<small>₂</small>O + He) with the aim to robustly date Palaeogene (66–23 Ma) molybdenite from the Bingham Canyon and Henderson deposits. CH<small>₄</small> mixed with H<small>₂</small> gas gives the highest sensitivity, while N<small>₂</small>O and He gas buffer Re reaction. On balance, the analytical method involving N<small>₂</small>O + He reaction gas is most suitable for dating Palaeogene molybdenite, resulting in age precision of 2.6% for Bingham and 5.8% for Henderson. For older, &gt;1 Ga molybdenite, CH<small>₄</small> + H<small>₂</small> + He may give comparatively better age precision.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1394-1402"},"PeriodicalIF":3.1,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913794","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}

{"title":"Precise and accurate Ga isotope analysis of solution standards and geological reference materials by MC-ICP-MS","authors":"Dandan Li, Zida Zhang, Xuesong Fan, Tianhao Wu, Zixuan Huang, Qianqian Shen, Xuefei Liu and Sheng-Ao Liu","doi":"10.1039/D5JA00070J","DOIUrl":"https://doi.org/10.1039/D5JA00070J","url":null,"abstract":"<p >Gallium (Ga) isotopes are being increasingly applied as a new geochemical tracer, but the modest variations in Ga isotope ratios in most of the geological samples necessitate precise and accurate Ga isotope analysis. Additionally, a unified reference material for Ga isotope analysis has yet to be established. Herein, we report a novel procedure for complete separation of Ga from matrices in geological samples using AG1-X8 and AG50W-X8 exchange resins with yields of &gt;99.5%. Isotope ratios were measured using a Neptune Plus multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) in low-resolution mode, employing internal standardization methods (C-SSBIN) for mass bias correction, and the results are reported as <em>δ</em><small>⁷¹</small>Ga in units per mil against NIST SRM 3119a. Two pure Ga solutions (NIST SRM 994 and GBW(E) 080560) were used as secondary reference materials during Ga isotope analysis, with <em>δ</em><small>⁷¹</small>Ga of −2.11 ± 0.05‰ (2SD, <em>n</em> = 106) and −1.00 ± 0.04‰ (2SD, <em>n</em> = 97) against NIST SRM 3119a, respectively. The Ga isotope compositions of a suite of geological reference materials (GSS-1, GSS-11, GSS-12, GXR-1, NIST SRM 2711a, GSD-12, NOD-P-1, BHVO-2, BCR-2, GSP-2, JG-1, JGb-2, GSR-1, GSR-6, AGV-2 and SGR-1b) were reported, with about half of them for the first time. The long-term external reproducibility is ±0.07‰ (2SD) based on replicated measurements of reference materials. Our results reveal that Ga isotopes are not significantly fractionated during igneous processes, although distinct variations are observed in gabbro and Mn nodules. Our analyses further confirm that NIST SRM 994 is isotopically heterogeneous with respect to Ga isotopes, and we recommend NIST SRM 3119a as the zero-point reference material for Ga isotope analysis.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1383-1393"},"PeriodicalIF":3.1,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913793","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}

{"title":"Nitrogen MICAP with post-plasma ionization mass spectrometry for elemental fluorine quantitation†","authors":"Jordan L. Tanen and Kaveh Jorabchi","doi":"10.1039/D5JA00059A","DOIUrl":"https://doi.org/10.1039/D5JA00059A","url":null,"abstract":"<p >Recent developments in high-power nitrogen microwave plasmas have made them attractive excitation and ionization sources for elemental analysis, offering robust operation with liquid sample introduction and significant cost savings. However, nonmetal detection, particularly F analysis, remains challenging with these plasmas because of their lower excitation and ionization temperatures compared to Ar-ICP while the need for elemental F analysis continues to rise due to prevalence of fluorochemicals in pharmaceuticals and environmental contaminants. Here, we combine the advantages of a N<small>₂</small> microwave inductively coupled atmospheric pressure plasma (MICAP) with those of post-plasma chemical ionization and evaluate the approach for elemental F analysis. The MICAP acts as a robust plasma reactor to break down fluorochemicals into HF which is then ionized to ScFNO<small>₃</small>(H<small>₂</small>O)<small>_<em>n</em></small><small>⁺</small> and detected by a quadrupole MS as ScF<small>⁺</small> after in-source ion activation. The approach offers a sensitivity of ∼18 cps ng<small>⁻¹</small> mL of F, superior to &lt; 4 cps ng<small>⁻¹</small> mL of F achieved by BaF<small>⁺</small> detection in Ar-ICP-MS/MS. An LOD of ∼40 ng mL<small>⁻¹</small> of F is obtained comparable to those of Ar-ICP-MS/MS, limited by background equivalent concentration likely dominated by F contamination. F response factors are also independent of chemical species when sample introduction biases are minimized. However, broadening of flow injection peaks over time is observed, especially with high oxygen levels in the aerosol gas, denoting future areas of improvement for better analytical performance. These studies indicate a high potential of MICAP with post-plasma chemical ionization for F quantitation.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1176-1184"},"PeriodicalIF":3.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00059a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High sensitivity detection of heavy metal elements in water by polishing assisted SE-LIBS","authors":"Qiuyun Wang, Xun Gao, Zeyu Wang, Ying Cui, Anmin Chen and Xueyan Han","doi":"10.1039/D5JA00096C","DOIUrl":"https://doi.org/10.1039/D5JA00096C","url":null,"abstract":"<p >This study presents a highly sensitive method for detecting heavy metals (Cr, Cu, and Pb) in water using surface-enhanced laser-induced breakdown spectroscopy (SE-LIBS) with a sandpaper-polished metal substrate. Solutions containing Cr, Cu, and Pb were applied to an Al metal substrate polished with 2000 mesh sandpaper. The polishing process reduced the “coffee ring effect”, promoting a more even distribution of elements, improving spectral stability, and minimizing experimental errors. The quantitative analysis results show that the detection limits of Cr, Cu and Pb were 1.02, 1.23 and 3.26 ng mL<small>⁻¹</small>. This method dramatically enhances the sensitivity, accuracy and stability of heavy metal detection, and plays a key role in water quality monitoring and environmental pollution analysis.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1411-1418"},"PeriodicalIF":3.1,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913796","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}

{"title":"Sensitive detection of trace precious metals in acidic solutions using liquid sheet jet laser-induced breakdown spectroscopy","authors":"Ryuzo Nakanishi, Morihisa Saeki and Hironori Ohba","doi":"10.1039/D4JA00467A","DOIUrl":"https://doi.org/10.1039/D4JA00467A","url":null,"abstract":"<p >Rapid <em>in situ</em> analysis of precious metals in liquid has been highly desired for real-time monitoring of recovery processes. We demonstrate that laser-induced breakdown spectroscopy (LIBS) combined with a liquid sheet jet provides a sensitive technique that can directly analyze trace precious metals (Au, Pt, Pd, Ag, Rh, and Ru) in acidic aqueous solutions. A glass slit nozzle resistant to corrosive acids was employed to generate a liquid sheet jet with a thickness of tens of micrometers, which mitigated the liquid splashing inherent in the direct detection of liquid by LIBS, thereby yielding persistent luminous plasma. The optimal thickness of the sheet jet for LIBS measurement was determined to be 14 μm. The LIBS spectral profiles for each analyte obtained by 532 nm laser excitation were explored to select the analytical lines for quantitative analysis. The univariate calibration curves of the analyte elements were then constructed to calculate the limits of detection (LODs) as well as other figures of merit. The LODs of Au, Pt, Pd, Ag, Rh, and Ru were estimated to be 0.62, 0.97, 0.09, 0.14, 0.09, and 0.15 mg L<small>⁻¹</small>, respectively, achieving detection limits below 1 mg L<small>⁻¹</small> and representing a significant improvement over conventional liquid jet LIBS. Thus, liquid sheet jet LIBS offers a useful tool for real-time monitoring of metal recovery processes.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1185-1191"},"PeriodicalIF":3.1,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913741","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}

{"title":"A digestion-purging-trapping method for precise stable mercury isotope measurements of natural carbonates†","authors":"Fei Cao, Ruoyu Sun, Larissa Schneider, Yongquan Zhang, Songjing Li, Rujia Yan, Shicheng Tao, Xiuyang Jiang, Pengfei Li, Wang Zheng, Jiubin Chen and Yi Liu","doi":"10.1039/D5JA00063G","DOIUrl":"https://doi.org/10.1039/D5JA00063G","url":null,"abstract":"<p >Natural carbonates, such as the aragonite of corals and calcite of speleothems, are potential archives of mercury (Hg) isotope signatures of freshwater and seawater. However, the ultra-low Hg levels in carbonates pose a great challenge for their isotopic analysis. In this study, we developed a digestion-purging-trapping protocol to separate and trap Hg from carbonates for high-precision isotope analysis for the first time. High Hg recovery (100 ± 6%) was achieved by digestion of the carbonate sample and followed by Hg(<small>II</small>) reduction and Hg(0) purging and trapping into sulfidic KMnO<small>₄</small>. Our protocol was validated by testing synthetic carbonates spiked with varying amounts of certified Hg standards and interfering ions. The protocol could handle large sample volumes (up to 20 grams) in a short processing time (∼30 min), achieving high precision (0.08‰ (2SD) for <em>δ</em><small>²⁰²</small>Hg), low blanks (&lt;40 pg), and limited matrix interference in Hg isotopic analysis. For facilitating interlaboratory comparison, we measured the Hg isotope compositions of two geological standards (GBW 07129: limestone and GBW 07134: dolostone). Our measurements of coral and speleothem samples showed characteristic Hg isotope signatures indicative of their forming environments, highlighting their potential to record long-term Hg cycling.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1373-1382"},"PeriodicalIF":3.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913792","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}

{"title":"Some considerations on thick sample thickness in X-ray fluorescence analysis","authors":"Paweł Wróbel and Filip J. Baran","doi":"10.1039/D4JA00406J","DOIUrl":"https://doi.org/10.1039/D4JA00406J","url":null,"abstract":"<p >In this work, the problem of the assessment of thickness for a thick sample in the case of polychromatic excitation has been considered. For a given sample composition, such a thickness (more precisely a product of the sample thickness and density) can be calculated easily in the case of monochromatic excitation—for which an analytical solution of the Sherman [J. Sherman, <em>Spectrochimica Acta</em>, 1955, <strong>7</strong>, 283–306]/Shiraiwa–Fujino [T. Shiraiwa and N. Fujino, <em>Japanese Journal of Applied Physics</em>, 1966, <strong>5</strong>, 886] equations can be found. For the polychromatic case, however, such a solution does not exist. In this work, some approximations of the problem are discussed and compared with a full solution acquired in an iterative way.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1164-1168"},"PeriodicalIF":3.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913698","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}

{"title":"Atomic spectrometry update: review of advances in atomic spectrometry and related techniques","authors":"E. Hywel Evans, Jorge Pisonero, Clare M. M. Smith and Rex N. Taylor","doi":"10.1039/D5JA90013A","DOIUrl":"https://doi.org/10.1039/D5JA90013A","url":null,"abstract":"<p >This review of 180 references covers developments in ‘Atomic Spectrometry’ published in the twelve months from December 2023 to November 2024 inclusive. It covers atomic emission, absorption, fluorescence and mass spectrometry, but excludes material on speciation and coupled techniques which is included in a separate review. It should be read in conjunction with the previous review<small>¹</small> and the other related reviews in the series.<small>^2–6</small> A critical approach to the selection of material has been adopted, with only novel developments in instrumentation, techniques and methodology being included. Automated chip-based methods for elemental tagging and amplification are being developed which promise to further bring this technique into routine operation. High resolution bioimaging using LA-ICP-MS is becoming more sophisticated due to finer control of the laser pulse and new methods developed to deal with the large amounts of data generated. Single particle analysis utilising ICP-MS continues to offer new developments, particularly when used in conjunction with elemental tagging and bioimaging; and a new hyphenated method for single particle analysis was reported which married optofluidic force induction, Raman spectroscopy and ICP-MS. New research on LIBS techniques continues to address the issues of matrix effects and calibration, liquid analysis and chemometric data treatment, driving the technique forward.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 5","pages":" 1136-1157"},"PeriodicalIF":3.1,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913696","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}