Journal of Analytical Atomic Spectrometry最新文献

{"title":"Graphene oxide mediated dispersive micro solid phase extraction (Dμ-SPE) and quantification of rare earth elements (REEs) from seawater and coal fly-ash by ICP-OES","authors":"D. Saikrishna, Vatsal Trivedi, G. Venkateswarlu, M. Sebastian, R. Shekhar and K. Dash","doi":"10.1039/D5JA00040H","DOIUrl":"https://doi.org/10.1039/D5JA00040H","url":null,"abstract":"<p >A novel graphene oxide (GO) mediated dispersive micro solid phase extraction method (Dμ-SPE) was developed for the extraction of rare earth elements (REEs) from seawater and digests of coal fly-ash, and the REE concentrations were determined using an inductively coupled plasma optical emission spectrometer (ICP-OES). This method involves the quantitative sorption of REE<small>³⁺</small> ions from the samples onto the negatively charged surface of GO through electrostatic interactions. The extraction was carried out in the pH range of 7–9, where GO acquires a negative surface charge due to de-protonation of surface functional groups such as –COOH. The increased number of reactive sites at higher pH for metal sorption improved its efficiency. The challenges posed in the separation of REE sorbed GO (REE-GO) were addressed by charge neutralization using an electrolyte, NaCl. The REE-GO was centrifuged and REE was ultrasonically back extracted into dilute nitric acid for their determination using ICP-OES. Under optimized conditions, the limits of detection for REEs were in the range of 10–50 ppb with a relative standard deviation of 5–8%. The method was successfully applied to the extraction of trace REEs in seawater matrices and leachates of different coal fly-ash samples. The sample preparation procedure with the GO nanoparticles was found to be simple and fast with good extraction recoveries.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2879-2887"},"PeriodicalIF":3.1,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196114","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":"In situ micro-beam U–Pb dating of apatite using CAMECA 1300HR3 LG-SIMS","authors":"Yue Guan, Jun-Yong Li, Allen K. Kennedy, De-Hong Du, Lan-Lan Tian, Wen-Li Xie and Xiao-Lei Wang","doi":"10.1039/D5JA00266D","DOIUrl":"https://doi.org/10.1039/D5JA00266D","url":null,"abstract":"<p >Apatite is a U-bearing mineral commonly present in planetary materials and has been widely used for geochronological studies. However, precise <em>in situ</em> U–Pb dating of tiny apatite (grain size &lt;15 μm) remains challenging due to its low abundance of uranium (U) and radiogenic lead (Pb). To address this issue, we have developed two micro-beam analytical methods (<em>i.e.</em>, 5 nA and 500 pA primary beams) using three apatite reference materials (BR5, AFG2, and Otter lake) and a CAMECA IMS 1300HR<small>³</small> large-geometry secondary ion mass spectrometry (LG-SIMS). The 5 nA method (mono) produces a larger sputter crater (12.5 × 12.5 × 4.1 μm) and achieves higher dating precision, with age errors (<em>n</em> = 20) of &lt;0.5% (1σ) for BR5, &lt;2.5% (1σ) for AFG2, and &lt;0.7% (1σ) for Otter lake. In contrast, the 500 pA method (multi) produces a smaller sputter crater (5.3 × 5.3 × 1.4 μm) that results in lower dating precision, with age errors (<em>n</em> = 25) of &lt;1.3% (1σ) for BR5, &lt;4.1% (1σ) for AFG2, and &lt;1.8% (1σ) for Otter lake. Both methods yield accurate ages within the uncertainties and are applicable for apatite U–Pb dating. For data reduction, we recommend the use of the Pb/U <em>vs.</em> UO<small>₂</small>/U calibration protocol, because it introduces less age bias compared to those of Pb/U <em>vs.</em> UO/U and Pb/UO <em>vs.</em> UO<small>₂</small>/UO protocols. The methodological approaches of this study enable high-precision <em>in situ</em> U–Pb dating of tiny apatite and they will expand the application of LG-SIMS in geochronological studies of (extra-) terrestrial apatite samples.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2753-2762"},"PeriodicalIF":3.1,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196069","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":"Kinetic analysis of boron therapeutics in head and neck cancer cells by complementary bulk ICP-MS and single-cell (scICP-MS) approaches","authors":"Jack G. Finch, Rhiannon J. Pass, Maria Rita Fabbrizi, Aimee E. P. McLoughlin, Stuart Green, Jason L. Parsons and James P. C. Coverdale","doi":"10.1039/D5JA00228A","DOIUrl":"https://doi.org/10.1039/D5JA00228A","url":null,"abstract":"<p >Boron neutron capture therapy (BNCT) is an emerging approach to radiotherapy. Neutron capture by a boronated (<small>¹⁰</small>B) therapeutic yields high linear energy transfer alpha particles (helium nuclei, <small>⁴</small>He) and lithium-7 (<small>⁷</small>Li) atoms, eliciting a localised cell kill effect. Current methods to quantify boron in cells either infer from circulatory concentrations and/or often overlook rapid boron pharmacokinetics. By considering both sample preparation requirements and biological boron dynamics, we report two novel approaches to quantify intracellular boron: firstly, rapid <em>in situ</em> tryptic and acidic digestion of treated cells to avoid premature B efflux (LOD <small>¹⁰</small>B<small>⁺</small> = 0.2 μg L<small>⁻¹</small>, LOD <small>¹¹</small>B<small>⁺</small> = 0.4 μg L<small>⁻¹</small>) with method suitability confirmed by pre- and post-digestion spike recoveries (102.5 ± 0.5% and 103 ± 3% recovery, respectively); secondly, real-time measurement of boron in live cells using single-cell ICP-MS (scICP-MS) revealing real-time monitoring of boron efflux: biological half-life of <em>ca.</em> 6 min. These complementary approaches deliver unprecedented insight into boron influx and efflux and provide essential bioanalytical tools to advance both BNCT therapeutic development and single-cell elemental analysis.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2763-2772"},"PeriodicalIF":3.1,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00228a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196070","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":"Accurate thresholding using a compound-Poisson-lognormal lookup table and parameters recovered from standard single particle ICP-TOFMS data","authors":"Thomas E. Lockwood, Raquel González de Vega, Lukas Schlatt and David Clases","doi":"10.1039/D5JA00230C","DOIUrl":"https://doi.org/10.1039/D5JA00230C","url":null,"abstract":"<p >The use of time-of-flight (TOF)-based instruments in single particle inductively coupled plasma-mass spectrometry (ICP-MS) is growing quickly. While these instruments have critical advantages over their quadrupole counterparts, they present new challenges when determining thresholding values in single particle analyses. One challenge is the need to analyse the single-ion area (SIA), which is essential for accurate thresholding in single particle data sets. However, the SIA is different for each element and changes across usage, time and during detector calibration. Rapid and effective algorithms are required to determine the SIA and predict thresholds automatically. Here we introduce new tools to investigate and fit the SIA with a lognormal distribution and, for determining background signal in single particle ICP-TOFMS. First, a lookup table of compound-Poisson-lognormal quantiles was computed using a simulation of 10<small>¹⁰</small> random values. This improved accuracy of thresholds at large lognormal standard deviations and was significantly faster than our previous approach. To facilitate its use, we have implemented it into our data processing software, SPCal. We also present a method to recover the SIA parameters that are required for thresholding from both raw ionic and particle data, enabling on-site SIA fitting during normal data processing. This method was tested both in simulation and experimentally, across different instruments, conditions and masses. The limitations of the method are discussed and conditions required for successful recovery determined.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2633-2640"},"PeriodicalIF":3.1,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00230c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196073","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":"Development of a matrix-matched standard for the elemental analysis of human hair by LA-ICP-MS","authors":"Kaitlyn Bonilla, Ashley Fox, Chloe Phillips and Matthieu Baudelet","doi":"10.1039/D5JA00242G","DOIUrl":"https://doi.org/10.1039/D5JA00242G","url":null,"abstract":"<p >Human hair as a biological matrix presents a detailed distribution profile of organic and inorganic components in the body. In comparison to blood and urine, hair introduces great advantages as it provides a temporal record with growth and longer detection window of analytes. Elemental analysis by LA-ICP-MS has been studied using different strategies for standards, however there is not a reference material that reproduces the physical and chemical properties of hair. This work demonstrates the development of a matrix-matched calibration standard using a keratin film doped with metals of interest for LA-ICP-MS analysis. The material was synthesized from extracted human hair keratin using the “Shindai method”, purified, spiked, and cross-linked to obtain a thin homogenous film. A series of calibration standards were prepared for trace concentrations of Ba, Pb, Mo, As, Zn, Mg, and Cu. Linear calibration models were built with limits of detection as low as 0.43 μg g<small>⁻¹</small> for Pb. The material was characterized by its thickness, homogeneity, and matrix-matching compared to human hair. The calibration materials were cross evaluated with spiked single human hairs for verification. These results provide a new set of standards for LA-ICP-MS to be used in internal medicine, forensic toxicology, and biological anthropology.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2745-2752"},"PeriodicalIF":3.1,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00242g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196068","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":"Correction: A novel in situ methodology for U–Pb, (U–Th)/He, and fission track triple dating","authors":"Jie Hu, Zhiwu Li, Jinxi Li, Shugen Liu, Ganqing Xu, Chaoqun Yang, Kui Tong and Yin Li","doi":"10.1039/D5JA90042E","DOIUrl":"https://doi.org/10.1039/D5JA90042E","url":null,"abstract":"<p >Correction for “A novel <em>in situ</em> methodology for U–Pb, (U–Th)/He, and fission track triple dating” by Jie Hu <em>et al.</em>, <em>J. Anal. At. Spectrom.</em>, 2024, <strong>39</strong>, 2856–2869, https://doi.org/10.1039/D4JA00257A.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2609-2609"},"PeriodicalIF":3.1,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja90042e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909594","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":"A novel (NH4)2HPO4–LiBO2 fusion technique for bulk silicate rock analysis by laser ablation-inductively coupled plasma-mass spectrometry","authors":"Xiaoyun Qiu, Zhaochu Hu, Tao Luo, Tao He, Wen Zhang, Ming Li, Zhenli Zhu, Lijin Huang and Mingxing Gong","doi":"10.1039/D5JA00205B","DOIUrl":"https://doi.org/10.1039/D5JA00205B","url":null,"abstract":"<p >Preparation of homogeneous and mechanically resistant targets is essential for representative bulk analysis using laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). Fused glasses are preferred (for LA-ICP-MS) over pressed powder pellets owing to their greater homogeneity. However, their use is often limited by the loss of Pb and Zn during the fusion process. In this study, a novel and rapid (NH<small>₄</small>)<small>₂</small>HPO<small>₄</small>–LiBO<small>₂</small> fusion technique using a homemade fusion furnace and graphite crucibles was established for determining major and trace elements in silicate rocks by LA-ICP-MS. Homogeneous glasses were produced by fusing a mixture of ∼50 mg of silicate rock powders, 10 mg of (NH<small>₄</small>)<small>₂</small>HPO<small>₄</small>, and 100 mg of LiBO<small>₂</small> at 950 °C for 5 min in a closed fusion system. This approach ensures the complete dissolution of refractory minerals such as zircon and effectively suppresses the loss of volatile elements such as Pb and Zn. The use of a 100% oxide normalization calibration strategy provided accurate results, enabling the direct analysis of unknown samples without any prior determination of internal standard element mass fractions. Analytical results for most elements in five silicate rock reference materials generally agreed with the reference values, within 10% deviation. Precision was achieved within 5% relative standard deviation (RSD) for major elements and 10% RSD for most trace elements. The developed method is simple, rapid, and efficient, addressing the challenges of volatile element loss and incomplete dissolution of refractory minerals, which significantly benefits the application of LA-ICP-MS for bulk silicate rock analysis.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2773-2782"},"PeriodicalIF":3.1,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196092","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":"Towards a chemical fingerprint of graphite by laser-induced breakdown spectroscopy†","authors":"Róbert Arató, Derrick Quarles, Gabriella Obbágy, Zsolt Dallos, Miklós Arató, Phillip Gopon and Frank Melcher","doi":"10.1039/D5JA00053J","DOIUrl":"https://doi.org/10.1039/D5JA00053J","url":null,"abstract":"<p >Graphite is a critical raw material for sustainable energy technologies, and establishing its traceability is crucial for ensuring responsible sourcing in the future. This study presents maps acquired on a comprehensive set of natural graphite concentrates <em>via</em> Laser-induced Breakdown Spectroscopy (LIBS). LIBS generates multi-elemental data at an unprecedented speed even from samples with non-ideal ablation characteristics, such as pressed graphite pellets. The generated data is used for constructing elemental maps to shed light on the chemical distribution of elements as well as for multivariate classification. Natural graphite concentrates exhibit inhomogeneous chemical composition. As such, the graphite concentrate LIBS-fingerprint is a heterogeneous mixture of LIBS signals from pure graphite and mineral impurities, which either represent crystal intergrowth with graphite, or they are adsorbed on graphite flakes as a result of natural or artificial processes. The observed chemical heterogeneity serves as a prominent fingerprint of individual deposits, although the heterogeneity is also omnipresent between different samples of the same deposit. The generated multivariate dataset is well suited for multivariate data analysis. Random forest classifiers show a robust performance across a broad range of hyperparameters, achieving over 90% classification accuracy. The heterogeneity of the concentrates presents a significant challenge for classification, regardless of the analytical and classification approach used. The addition of chemically different samples to the same classification group (<em>i.e.</em>, graphite deposit) does not necessarily hinder correct classification and renders the routine application of the method possible.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2526-2537"},"PeriodicalIF":3.1,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00053j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909597","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":"Development of a SEC-ICP-MS platform for multielement metallobiomolecule profiling and quantitation using a blood serum reference material","authors":"Georgia Panagou, Nikos Lydakis-Simantiris and Spiros A. Pergantis","doi":"10.1039/D5JA00182J","DOIUrl":"https://doi.org/10.1039/D5JA00182J","url":null,"abstract":"<p >The characterization of metallobiomolecules in biological fluids is essential for understanding metal homeostasis, biomarker discovery, as well as toxicity assessment. In this work, we present a size-exclusion chromatography inductively coupled plasma mass spectrometry (SEC-ICP-MS) platform for the comprehensive profiling of metallobiomolecules in human serum. This method enables the simultaneous detection and quantitation of ten metals and metalloids (Co, Mg, Ca, Cu, Zn, Fe, Mn, Pb, Se, Hg) within a single sample. The integration of post-column flow injection allows for element calibration, using ionic standards containing EDTA, total element determination following the injection of an acid-diluted blood serum sample, and instrument sensitivity monitoring and correction. Method validation was performed using the certified total element concentration in a human reference material (Seronorm Trace Elements Level 2). Element recoveries exceeded 80% for most analytes, both following total element determination and column elution, confirming the robustness and accuracy of the approach. An on-column EDTA injection strategy effectively mitigated metal/metalloid interactions with the stationary phase, enhancing column recoveries of Co and Zn while preventing cross-contamination between samples. This platform expands the number of elements that can be simultaneously monitored and quantified, and maximizes the information obtained for the analysis of each sample, providing an improved assessment of metal/metalloid distributions in human blood serum. The analysis of Seronorm Trace Elements Level 2 material provided novel insights into the element distribution across different relative molecular mass metallobiomolecules. Detected metallobiomolecule bands aligned with biomolecules known to be present in human serum and previous studies of this reference material, yet discrepancies in element distribution suggest possible element addition during reference material preparation. Its ability to provide detailed elemental distributions across biomolecular bands enhances its potential for applications in biomarker discovery, disease monitoring, and environmental exposure assessments.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2582-2598"},"PeriodicalIF":3.1,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00182j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909584","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":"Mechanism of elemental fractionation during femtosecond laser ablation revealed by high-time-resolution MC-ICP-MS analysis of 208Pb/232Th ratios in single particles","authors":"Sota Niki and Takafumi Hirata","doi":"10.1039/D5JA00016E","DOIUrl":"https://doi.org/10.1039/D5JA00016E","url":null,"abstract":"<p >This study investigated the mechanism of elemental fractionation during laser ablation (LA) through elemental analysis of individual particles generated <em>via</em> femtosecond laser ablation (fsLA) using a minimised laser spot size of approximately 2 μm. Data acquisition was conducted within a short dwell time of 20 μs using a multiple collector-ICP-mass spectrometer equipped with a high-time-resolution ion counting system (HTR-MC-ICP-MS), which avoids the overlap of signal events from multiple particles. Results obtained from monazite references showed that individual fsLA-generated particles fall into two distinct groups in terms of <small>²⁰⁸</small>Pb/<small>²³²</small>Th: Pb-bearing (volatile-element-rich) <em>vs.</em> Pb-depleted (volatile-element-poor). The existence of these two populations is probably the major cause of elemental fractionation in LA. This decoupling is attributed to the different behaviours of volatile and refractory elements during particle generation. Particles that condense from laser-induced vapor plume tend to retain volatile elements (<em>e.g.</em>, Pb), whereas particles originating from the molten rim of the ablation pit (material that was molten but not vaporized) are depleted in volatile elements. The data obtained here clearly demonstrated that elemental fractionation is involved in the particle generation process, and hence, using matrix-matched reference materials is essential for obtaining reliable elemental data in LA-ICP-MS.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2716-2724"},"PeriodicalIF":3.1,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196065","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}