Journal of Analytical Atomic Spectrometry最新文献

{"title":"No significant crystal orientation effect during sulfur isotope analysis of marcasite using SIMS†","authors":"Rucao Li, Jinyu Yan, Jianwei Yu, Xiao-Lei Wang, Tao Yang, Shengping Qian, Chengming Wang and Haiyang Xian","doi":"10.1039/D4JA00367E","DOIUrl":"https://doi.org/10.1039/D4JA00367E","url":null,"abstract":"<p >The sulfur isotopic composition of marcasite (FeS<small><sub>2</sub></small>, orthorhombic), a dimorph of pyrite (FeS<small><sub>2</sub></small>, isometric), can be used to trace ore-forming fluid source(s) and ocean acidification events in deep time. However, matrix-matched standards for marcasite are scarce, and in practice, a pyrite standard is commonly used to calibrate the sulfur isotope ratio of marcasite during laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) and secondary ion mass spectrometry (SIMS) analyses. Recently, it has been suggested that it is feasible to calibrate the sulfur isotope ratio of marcasite with a pyrite standard during SIMS analysis, but the crystal orientation effect during sulfur isotope analysis of marcasite using SIMS remains unexplored. We investigated this topic by analyzing a natural marcasite sample (NJUMc-1). We analyzed NJUMc-1 using LA-MC-ICP-MS and SIMS. The analysis spots for LA-MC-ICP-MS and SIMS were very close to each other, and both spots were located in domains with the same brightness in backscattered electron images (BSE). The results derived from these two methods lie around a 1 : 1 line in a <em>δ</em><small><sup>34</sup></small>S<small><sub>LA-MC-ICP-MS</sub></small><em>vs. δ</em><small><sup>34</sup></small>S<small><sub>SIMS</sub></small> binary diagram, indicating that SIMS data are comparable to LA-MC-ICP-MS data. However, there are some grains in which <em>δ</em><small><sup>34</sup></small>S<small><sub>LA-MC-ICP-MS</sub></small> deviates from <em>δ</em><small><sup>34</sup></small>S<small><sub>SIMS</sub></small> (“<em>δ</em><small><sup>34</sup></small>S<small><sub>LA-MC-ICP-MS_NJU</sub></small> − <em>δ</em><small><sup>34</sup></small>S<small><sub>SIMS</sub></small>” >+2‰ or <−2‰). This discrepancy possibly indicates a crystal orientation effect during SIMS analysis. To confirm whether there is a crystal orientation effect during SIMS analysis, we conducted a second round of LA-MC-ICP-MS analysis in Beijing and selected two sets of NJUMc-1 marcasite grains and conducted electron backscatter diffraction (EBSD) analysis. For the first set of NJUMc-1 grains, characterized by variable “<em>δ</em><small><sup>34</sup></small>S<small><sub>LA-MC-ICP-MS_Beijing</sub></small> − <em>δ</em><small><sup>34</sup></small>S<small><sub>SIMS</sub></small>” values, there is no correlation between crystal orientation and “<em>δ</em><small><sup>34</sup></small>S<small><sub>LA-MC-ICP-MS_beijing</sub></small> − <em>δ</em><small><sup>34</sup></small>S<small><sub>SIMS</sub></small>” values. For the second set of NJUMc-1 grains, characterized by “<em>δ</em><small><sup>34</sup></small>S<small><sub>LA-MC-ICP-MS_Beijing</sub></small> − <em>δ</em><small><sup>34</sup></small>S<small><sub>SIMS</sub></small>” values around 0‰, highly variable crystal orientations are observed. These findings suggest that if a crystal orientation effect exists during SIMS analysis, it should b","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 775-784"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553605","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":"Data augmentation using GANN in the quantitative LIBS analysis of scarce samples: a case study on polymetallic nodules from 5000 m ocean depth","authors":"Jie Ren, Suming Jiang, Chen Sun, Zhenggang Li, Yanhui Dong, Ling Chen, Xibin Han, Jin Yu and Wendong Wu","doi":"10.1039/D4JA00412D","DOIUrl":"https://doi.org/10.1039/D4JA00412D","url":null,"abstract":"<p >As the world transitions towards renewable energy, the demand for critical resources such as nickel (Ni), cobalt (Co), and lithium (Li) in energy storage systems is ever more pronounced. The abundance of these elements in deep-sea polymetallic nodules provide an alternative to the land-based resources. However, the scarcity of deep-sea nodule samples poses a challenge in obtaining sufficient Laser-Induced Breakdown Spectroscopy (LIBS) data to train machine learning models for quantitative analysis. In this work, a Generative Adversarial Neural Network (GANN) with physical loss constraints was designed to augment the spectral database. Unsupervised classification techniques, including Principal Component Analysis (PCA) and Density-Based Spatial Clustering of Applications with Noise (DBSCAN), were employed to assess the similarity between experimental and generated spectra. Four machine learning models—Backpropagation Neural Networks (BPNN), Support Vector Machines (SVM), Extreme Gradient Boosting (XGBoost), and Convolutional Neural Networks (CNN)—were selected to represent a broad spectrum in current machine learning methods. Both experimental and expanded spectral datasets were used to train these models in quantitative elemental analysis. The model prediction performance was validated by comparing the results with those of inductively coupled plasma mass spectrometry (ICP-MS). The results demonstrated that augmenting the spectral database with GANN generated spectra improves the accuracy of machine learning models in the quantitative analysis of Ni, Co, and Li in deep-sea polymetallic nodules, providing a valuable approach for LIBS-based analysis of scarce samples.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 825-835"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553630","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":"Analytical-performance enhancement of laser-induced breakdown spectroscopy using an annular laser beam","authors":"Bo Dai, Jingge Wang, Mianyun Ye, Yonghao Han and Hehe Li","doi":"10.1039/D4JA00445K","DOIUrl":"https://doi.org/10.1039/D4JA00445K","url":null,"abstract":"<p >In this paper, an axicon and a spherical lens were used to convert a circular Gaussian beam into an annular beam. Plasma was produced by a Q-switched Nd:YAG laser from an alloy steel sample with the annular beam. The spectral characteristics and analytical performance of trace elements using annular and Gaussian beam laser-induced breakdown spectroscopy (LIBS) were compared. The annular beam produced a larger stable plasma region with a flat spatial distribution. A 2–3 times enhancement in spectral stability was observed, while detection sensitivity increased by 2.1 times and the limit of detection (LoD) was reduced by 38.5%. The results of this study demonstrated that the plasma induced by an annular laser beam provides a new method to improve the analytical performance of LIBS.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 879-887"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553634","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":"High intermediate precision rhenium isotopic measurements in geological samples","authors":"Jinhua Liu, Lian Zhou, Xiang Wang, Jianwei Li, Thomas J. Algeo and Xiaodong Deng","doi":"10.1039/D4JA00267A","DOIUrl":"https://doi.org/10.1039/D4JA00267A","url":null,"abstract":"<p >Stable rhenium (Re) isotopes are important tracers for geological processes related to melting and differentiation of planetary interiors, ore mineralization and paleoenvironmental redox conditions. However, methods for the precise determination of Re isotope ratios have received limited investigation to date due to the extremely low Re mass fractions of most geological materials. In this study, we present a new protocol for increased intermediate precision in the measurement results of Re isotope ratios in geological materials using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Preconcentration of Re is an essential first step, involving digestion of 1–2 g of sample powder by concentrated NH<small>₃</small> solution, followed by coprecipitation of matrix ions other than Re, Mn and Mo. Subsequent purification and extraction of Re from the residual matrix was performed on TEVA resin. This approach provided an efficient purification with a low blank (&lt;0.2 pg) and high yield of Re (93.2 ± 2.4%, 2s, <em>n</em> = 5) for reference materials BCR-2 and TDB-1. Instrumental mass bias was monitored and corrected through a combination of standard-sample bracketing (SSB) and internal normalization of Ir as a calibration standard. This approach yielded about a two-fold improvement in the intermediate precision relative to SSB alone. In addition, a further two-fold improvement in precision was obtained by the use of a membrane desolvation system which can increase the intensity of Re isotopic signals by an order of magnitude. This protocol improved the intermediate precision of measured δ<small>¹⁸⁷</small>Re<small>_SRM3143</small> for a 1 ng g<small>⁻¹</small> Re analyte solution to 0.048‰. The δ<small>¹⁸⁷</small>Re<small>_SRM3143</small> of USGS basalt reference materials were measured using this measurement procedure, yielding δ<small>¹⁸⁷</small>Re<small>_SRM3143</small> of −0.31 ± 0.04‰ (2s, <em>n</em> = 6), −0.33 ± 0.05‰ (2s, <em>n</em> = 3), −0.35 ± 0.05‰ (2s, <em>n</em> = 3) for BCR-2, BHVO-2, BIR-1a, respectively, in agreement with values obtained in previous studies. Other reference materials were analyzed, yielding δ<small>¹⁸⁷</small>Re<small>_SRM3143</small> of −0.35 ± 0.05‰ (2s, <em>n</em> = 2), −0.36 ± 0.04‰ (2s, <em>n</em> = 3) and −0.31 ± 0.03‰ (2s, <em>n</em> = 3) for diabase (TDB-1), komatikic basalt (OKUM), and andesite (AGV-2), respectively. The developed procedure was successfully applied to measurement of samples with low Re mass fractions, extending the range of geological materials for which Re isotopic values can be determined.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 868-878"},"PeriodicalIF":3.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553633","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":"High-precision measurement of Eu isotopes enabled by Nd internal normalization†","authors":"Hao Wu, Jiang-Hao Bai, Xi-Rong Liang, Xi-Bin Lu, Yong-Ying Li, Yi-Nan Deng, Ye Zhao and Gang-Jian Wei","doi":"10.1039/D4JA00420E","DOIUrl":"https://doi.org/10.1039/D4JA00420E","url":null,"abstract":"<p >Eu isotopes are recognized as potential indicators for understanding continental crust evolution, ocean circulation, and rare earth element mineralization. However, methods for achieving high-precision Eu isotopic analysis remain underdeveloped. This study pioneers a comprehensive application of the Nd internal normalization technique in Eu isotope analysis, facilitating high-precision measurements of Eu isotope compositions in geological reference materials. It assesses the correction effectiveness of various Nd isotopic ratios (<small>¹⁴⁶</small>Nd/<small>¹⁴⁴</small>Nd, <small>¹⁴⁶</small>Nd/<small>¹⁴⁵</small>Nd, and <small>¹⁵⁰</small>Nd/<small>¹⁴⁸</small>Nd) on Eu isotopic measurements and investigates the fractionation behavior of Eu–Nd in mass spectrometers. These findings demonstrate that the <small>¹⁴⁶</small>Nd/<small>¹⁴⁵</small>Nd ratio significantly enhances the stability and reproducibility of Eu isotope measurements, achieving a long-term external precision of <em>δ</em><small>^153/151</small>Eu at 0.04‰ (2SD). Additionally, the study reveals that the fractionation behavior of Eu–Nd in mass spectrometry theoretically aligns more closely with the power law rather than the traditionally assumed exponential law. However, in practical tests, no significant difference in results is observed whether employing the power law or the exponential law. These insights advance Eu isotope geochemistry and provide a valuable reference for the high-precision analysis of other rare earth elements.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 860-867"},"PeriodicalIF":3.1,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553632","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":"Second version of the open-source software GSA for gamma-ray spectrum analysis","authors":"Lahcen El Amri, Hamid Amsil, Omar El Bounagui, Abdelouahed Chetaine, Brahim Elmokhtari, Hamid Bounouira and Abdessamad Didi","doi":"10.1039/D4JA00398E","DOIUrl":"https://doi.org/10.1039/D4JA00398E","url":null,"abstract":"<p >The collaboration among the PRESN team, LaMCScI laboratory and CNESTEN center made it possible to implement the first version of the GSA software. Its first version is already available to the public; it is not only free but also an open source, demonstrating the developers' commitment to promoting the open sharing of scientific knowledge. This first version is characterized by its flexibility and non-commerciality, and it is available without any conditions on the following website: https://www.github.com/LAHCEN-EL-AMRI/Gamma-Spectra-Analysis, allowing users to add personal options, making it a particularly adaptable tool to the different requirements of scientific research. This article deals with the second version of GSA, which focuses on a core and complementary feature: the calculation of isotope activity. In order to accomplish this goal, instead of implementing a single efficiency formula, as is often the case in most software, four formulas were integrated. The users can therefore select the one they want to implement. To ensure the accuracy and reliability of this new feature, a validation was performed on GSA. The results obtained with GSA v2 were carefully studied by comparing them to those obtained with the renowned Genie 2000 software. Owing to this comparison step, it was possible to verify and confirm the accuracy of the results of GSA version 2. This second version of GSA is available as a free and open source software on the following site: https://www.github.com/LAHCEN-EL-AMRI/GSA-v2/tree/master.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 738-746"},"PeriodicalIF":3.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553602","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 ray tracing survey of asymmetric operation of the X-ray Rowland circle using spherically bent crystal analyzers","authors":"Yeu Chen, Anthony J. Gironda, Yaxin Shen, André D. Taylor and Gerald T. Seidler","doi":"10.1039/D4JA00339J","DOIUrl":"https://doi.org/10.1039/D4JA00339J","url":null,"abstract":"<p >The Spherically Bent Crystal Analyzer (SBCA) is a widely adopted hard X-ray optic, renowned for its good energy resolution and large collection solid angle. It is frequently employed in synchrotron-based techniques like Resonant Inelastic X-ray Scattering (RIXS) and X-ray Emission Spectroscopy (XES), as well as in the rebirth of laboratory-based X-ray Absorption Fine Structure (XAFS) and XES, and its predominant use has been in ‘symmetric’ operation on the Rowland circle. The recent study of Gironda <em>et al.</em> (<em>J. Anal. At. Spectrom.</em>, 2024, <strong>39</strong>, 1375) emphasizes the benefits of ‘asymmetric’ SBCA operation, demonstrating the use of multiple crystal reflections from a single SBCA to broaden its accessible energy range. Furthermore, Gironda <em>et al.</em> demonstrate that asymmetric operation frequently mitigates energy broadening intrinsic to Johann optics and propose that under a specific Rowland circle configuration, designated here the Johann Normal Alignment (JNA), such broadening is eradicated altogether. We report extensive ray tracing simulations and new experimental results to scrutinize the impact of asymmetric configurations on energy broadening and detector plane defocusing. We find that the performance of asymmetric SBCA operation generally exceeds its symmetric counterpart in energy resolution when no analyzer masking is used and, with strategic detector placement, the decrease in detection efficiency due to defocusing can be minimized. Spectroscopic imaging is adversely affected by the detector plane blurring, but rejection of scattering from special environment windows in X-ray Raman imaging is still feasible and high imaging quality can be recovered by Johann-like analyzer edge masking. These results help inform future, more common implementation of asymmetric reflections with SBCA in several synchrotron applications and in laboratory-based XAFS and XES.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 836-847"},"PeriodicalIF":3.1,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553631","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 selection tool for asymmetric reflections of spherically bent crystal analyzers for high resolution X-ray spectroscopy","authors":"Jared E. Abramson, Yeu Chen and Gerald T. Seidler","doi":"10.1039/D4JA00340C","DOIUrl":"https://doi.org/10.1039/D4JA00340C","url":null,"abstract":"<p >High resolution, hard X-ray spectroscopy at synchrotron X-ray light sources commonly uses spherically bent crystal analyzers (SBCAs) formed by shaping a single crystal wafer to a spherical backing. These Rowland circle optics are almost always used in ‘symmetric’ (or nearly symmetric) configurations wherein the reciprocal lattice vector used for energy selectivity <em>via</em> diffraction is coincident with the normal vector to the curved wafer surface. However, Gironda, <em>et al.</em>, <em>J. Anal. At. Spectrom.</em>, 2024, <strong>39</strong>, 1375–1387 recently proposed that asymmetric operation of SBCAs, wherein the reciprocal lattice vector is no longer normal to the wafer surface, has significant operational benefits and has been an underutilized opportunity. First, those authors find improved energy resolution through decreased Johann error, or equivalently find increased solid angle at a chosen experimental tolerance for energy broadening. Second, they find productive, high-resolution use of a large number of reciprocal lattice vectors from a single SBCA, thus enabling operation over a wide energy range without need to exchange SBCA upon making large changes in desired photon energy. These observations hold the potential to improve performance, increase flexibility and decrease cost for both laboratory and synchrotron applications. Given these motivations, we report an open-source software package, <img>, that enables exploration of the complex space of analyzer wafer choice, experimental energy range or ranges, and desired suppression of Johann error. This package can guide both the design and the day-to-day operations of Rowland spectrometers enabled for asymmetric use.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 817-824"},"PeriodicalIF":3.1,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553615","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":"Novel calibration approach for particle size analysis of microplastics by laser ablation single particle-ICP-MS†","authors":"Lukas Brunnbauer, Laura Kronlachner, Elias Foisner and Andreas Limbeck","doi":"10.1039/D4JA00351A","DOIUrl":"10.1039/D4JA00351A","url":null,"abstract":"<p >The need to analyze and characterize microplastics (MPs) is ever-increasing to monitor and understand their environmental impact. In this work, a developed calibration approach that utilizes an in-house-created polystyrene (PS) thin film for the sizing of MPs is presented, circumventing the need for certified particulate standard material. LA was used for sampling and transporting intact MPs of different sizes and polymer types to the ICP-MS. For the calibration, defined amounts of carbon were introduced into the ICP-MS by quantitatively ablating a polymer thin film with different laser spot sizes. With this approach, a LOD of 4.85 pg carbon was obtained, which translates to a size of 2.12 μm for spheric PS particles. The calibration using PS thin film was successfully applied to sampled PS MPs and allowed accurate sizing of 2 μm, 3 μm, and 4.5 μm particles. When using the PS calibration for determining polyvinyl chloride (PVC) and poly(methyl methacrylate) (PMMA) particle sizes, a good estimate of the size could be achieved despite the different compositions of the polymers. This indicates the universal applicability of the presented approach. The investigation of the transport efficiency showed that it is mainly influenced by particle size, and factors such as the polymer type and length of the transport line and carrier gas. Under optimum conditions, up to 95% of the sampled particles were detected.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 753-761"},"PeriodicalIF":3.1,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11783204/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143078014","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":"An emergency radiobioassay method for Pu, Am and Cm isotopes in urine samples using tandem quadrupole ICP-MS†","authors":"Yang Wu, Xiongxin Dai, Maoyi Luo, Hongmei Guo, Ni Yuan, Yonggang Yang, Jingjing He and Yuanyuan Guo","doi":"10.1039/D4JA00279B","DOIUrl":"https://doi.org/10.1039/D4JA00279B","url":null,"abstract":"<p >The rapid bioassay method for measuring actinides in human urine samples is the most appropriate way for the assessment of internal exposure doses during radiological and nuclear emergencies. A rapid simultaneous analysis method for <small>²³⁹</small>Pu, <small>²⁴⁰</small>Pu, <small>²⁴¹</small>Am and <small>²⁴⁴</small>Cm in 100 mL urine samples was established by using tandem quadrupole ICP-MS (ICP-MS/MS), combined with a hydrous titanium oxide (HTiO) co-precipitation step and a tandem small size resin column (TEVA + DGA) purification step for shortening the sample processing time. The ICP-MS/MS measurements of Pu isotopes, <small>²⁴¹</small>Am and <small>²⁴⁴</small>Cm were optimized in Q3 only mode and MS/MS mode, respectively, and the interferents from the urine matrix were appropriately suppressed by applying Axial Field Voltage (AFT). The measurement sensitivities of Pu and Am isotopes were improved by employing NH<small>₃</small> or He as collision/reaction cell gases, and an interesting finding is that pure NH<small>₃</small> significantly improved the Pu measurement sensitivity. The detection limits for the method were estimated to be 1.12 fg (2.57 × 10<small>⁻³</small> mBq) for <small>²³⁹</small>Pu, 0.97 fg (8.14 × 10<small>⁻³</small> mBq) for <small>²⁴⁰</small>Pu, 1.46 fg (0.19 mBq) for <small>²⁴¹</small>Am and 0.74 fg (2.16 mBq) for <small>²⁴⁴</small>Cm in 100 mL urine, meeting the sensitivity requirements for emergency urine bioassay methods.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 2","pages":" 513-519"},"PeriodicalIF":3.1,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143184588","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}