Journal of Analytical Atomic Spectrometry最新文献

{"title":"Particle signal considerations for isotope ratio analysis with single particle multi-collector inductively coupled plasma mass spectrometry†‡","authors":"Sarah E. Szakas, Jordan S. Stanberry, N. Alex Zirakparvar, Hunter B. Andrews, Daniel R. Dunlap, Matt Darnell, Brian W. Ticknor, Lorianne R. Shultz-Johnson, Shawna K. Tazik and Benjamin T. Manard","doi":"10.1039/D5JA00107B","DOIUrl":"https://doi.org/10.1039/D5JA00107B","url":null,"abstract":"<p >Particle analysis has benefitted from the advent of single particle inductively coupled plasma-mass spectrometry (spICP-MS) due to its robustness, sensitivity, and high-throughput nature. Previous methods of spICP-MS have typically utilized quadrupole or time-of-flight mass analyzers and therefore employ electron multiplier-based detectors (such as secondary electron multipliers or microchannel plates). However, to obtain precise measurements on elemental or isotopic ratios within individual particles, multi-collector ICP-MS (MC-ICP-MS) can be used. Here, we investigate Ce isotope ratios, specifically <small>¹⁴²</small>Ce/<small>¹⁴⁰</small>Ce, by spMC-ICP-MS using an all-Faraday cup collector array. Using 1 μm (diameter) cerium dioxide particles, integration times of the Faraday cup detectors were varied from 50–500 ms. The signal from the cerium isotopes in the particles was used to determine isotope ratios, which closely matched the expected natural isotopic abundances. Due to the signal decay response from the Faraday cups, the signal from particles lasts much longer than the expected 1–2 ms (up to 100 s of ms). To explore this effect on isotope ratio analysis, multiple ratio analysis methods were used to determine how to obtain optimal precision and accuracy. Relative differences were around 2% for methods that calculated isotope ratios from summing the total signal of an individual particle before calculating the ratio (rather than using every data point individually). It was found that summing all data points per particle, or integrating under the signal peak, yielded both accurate and precise isotope ratios within the particle population. Particles were also sampled off a solid substrate <em>via</em> microextraction, and isotope ratios were determined with relative differences of 0.13% to 9%. This demonstrates the ability to use spMC-ICP-MS to obtain isotope ratios on particles, with little to no relative difference in comparison to the expected ratio, even when operating Faraday detectors at fast 50 ms integration times.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 6","pages":" 1483-1493"},"PeriodicalIF":3.1,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00107b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144213743","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":"Depth profiling of noble gases in ilmenite and olivine substrates†","authors":"Yuta Otsuki, Ken-ichi Bajo, Tomoya Obase and Hisayoshi Yurimoto","doi":"10.1039/D4JA00430B","DOIUrl":"https://doi.org/10.1039/D4JA00430B","url":null,"abstract":"<p >Solar wind noble gases in extraterrestrial materials provide important insights into past solar activity and space weathering processes. These noble gases are concentrated within the uppermost 100 nm of material surfaces, requiring <em>in situ</em> analysis with high depth and lateral resolution. Additionally, the multi-isotope analysis of noble gases is useful in evaluating the degassing of materials. To address these requirements, we developed a depth profiling method for multi-noble gas isotopes by time-of-flight secondary neutral mass spectrometry. We prepared ilmenite and olivine substrates co-implanted with <small>⁴</small>He, <small>²⁰</small>Ne, <small>²²</small>Ne, <small>³⁶</small>Ar, and <small>⁴⁰</small>Ar as standards for solar wind-irradiated materials and surveyed the optimal analytical conditions to improve the substrate detection limits. As a result, we achieved <small>⁴</small>He, <small>²⁰</small>Ne, <small>²²</small>Ne, <small>³⁶</small>Ar, and <small>⁴⁰</small>Ar detection limits of 7 × 10<small>¹⁶</small>, 3 × 10<small>¹⁶</small>, 9 × 10<small>¹⁵</small>, 2 × 10<small>¹⁶</small>, and 5 × 10<small>¹⁶</small> cm<small>⁻³</small> for ilmenite and 2 × 10<small>¹⁷</small>, 4 × 10<small>¹⁶</small>, 2 × 10<small>¹⁶</small>, 2 × 10<small>¹⁶</small>, and 9 × 10<small>¹⁷</small> cm<small>⁻³</small> for olivine, respectively. The reproducibility for the concentration and elemental/isotope ratio measurements ranged from 5% to 31%. This method allowed for the visualization of nano-scale solar wind noble gas distributions on extraterrestrial material surfaces, providing insights into the solar wind activities and space weathering of celestial bodies.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 6","pages":" 1505-1517"},"PeriodicalIF":3.1,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d4ja00430b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144213745","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":"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":"Study on the identification of soybean origins combining laser-induced breakdown spectroscopy and convolutional neural networks","authors":"Li Wang, Tolok Galina, Longkun Jing, Li Xu, Yuanxia Fu, Hui Gao and Li Li","doi":"10.1039/D5JA00116A","DOIUrl":"https://doi.org/10.1039/D5JA00116A","url":null,"abstract":"<p >This study integrates Laser-Induced Breakdown Spectroscopy (LIBS) with CNNs to classify soybeans from five regions in China: Shandong, Heilongjiang, Guizhou, Zhejiang, and Neimenggu. A dataset of 650 samples was constructed, with 130 samples from each region. High-resolution spectral data were obtained using a customized LIBS system with optimized acquisition settings. After preprocessing—including noise reduction and feature selection—12 key spectral features were identified. The dataset was then split into a training set (265 samples) and a test set (110 samples), ensuring balanced representation. A CNN model was developed to automatically extract and classify spectral features. The model achieved 99.09% accuracy on the test set, significantly outperforming traditional machine learning models such as random forest and SVM. This demonstrates the effectiveness of combining LIBS with CNNs for the rapid and accurate identification of soybean origins. The approach offers promising applications in food quality control, traceability, and safety. The LIBS-CNN framework also opens new avenues for applying spectroscopic techniques with deep learning in fields such as authenticity verification, environmental monitoring, and materials science.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 6","pages":" 1526-1535"},"PeriodicalIF":3.1,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144213678","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}