Grace N. Manestar, Hilary M. K. Lewis, Alex McCoy-West, Nishen Naidoo, Stefan Makart, Ondrea Thompson and Brandon Mahan
Radiogenic strontium (87Sr/86Sr) is a powerful tool for characterizing and differentiating water reservoirs (among many other applications). The development and improvement of high-precision analytical platforms (namely MC-ICP-MS) has enhanced throughput for isotope ratio determination. However, analyte purification—needed to remove isobaric interferences—continues to occur largely via conventional manual gravity-driven ion exchange chromatography (hereafter: manual IEC), which generally cannot match instrument throughput. This has created a persistent throughput gap that encumbers use and proliferation, emphasizing the need for rapid separation of Sr, and of comprehensive, end-to-end high throughput workflows and analytical approaches that are fit-for-purpose. Here we have developed a workflow-optimized protocol for sample preparation and separation of Sr from natural water samples using both workflow-optimized manual IEC and automated high pressure ion chromatography (HPIC), for subsequent analysis via MC-ICP-MS. These methods have been designed to seamlessly integrate with common international practice for water sample collection. The automated HPIC technique accommodates introduction of water samples filtered with standard 0.45 μm membranes and acidified with ultra-high purity nitric acid (HNO3, to pH of 1–2, approximated as 0.09 mol per L HNO3). Filtered and acidified samples are directly introduced into the HPIC system where Sr is separated from other cations (namely Ca) and collected as an isolate in a specific volume of ultrapure water. Strontium isolates, with no further preparation (e.g. dry-down and reflux), are then directly acidified to 0.5 mol per L HNO3 and analyzed by MC-ICP-MS. This technique can process 40–50 samples in a 24 hour period with mitigated potential for human error, matching current MC-ICP-MS analytical capacity, and achieving analytical precision sufficient to distinguish the variability observed in natural samples across many applications.
放射性成因锶(87Sr/86Sr)是表征和区分水库(以及许多其他应用)的有力工具。高精度分析平台(即MC-ICP-MS)的发展和改进提高了同位素比测定的通量。然而,分析物纯化-需要消除等压干扰-仍然主要通过传统的手动重力驱动离子交换色谱(以下简称:手动IEC)进行,通常无法匹配仪器吞吐量。这造成了持续的吞吐量差距,阻碍了使用和扩展,强调了对Sr的快速分离,以及全面的,端到端高吞吐量工作流和适合用途的分析方法的需求。在这里,我们开发了一种工作流程优化的方案,用于样品制备和天然水样中Sr的分离,使用工作流程优化的手动IEC和自动化高压离子色谱(HPIC),随后通过MC-ICP-MS进行分析。这些方法的设计与水样采集的国际惯例无缝结合。自动化HPIC技术适用于引入用标准0.45 μm膜过滤并用超高纯度硝酸(HNO3, pH为1-2,近似为0.09 mol / L HNO3)酸化的水样。过滤和酸化后的样品直接导入HPIC系统,其中Sr与其他阳离子(即Ca)分离,并在特定体积的超纯水中作为分离物收集。分离的锶,无需进一步制备(如干燥和回流),然后直接酸化至0.5 mol / L HNO3,并通过MC-ICP-MS进行分析。该技术可以在24小时内处理40-50个样品,减少人为错误的可能性,匹配当前MC-ICP-MS的分析能力,并达到足够的分析精度,以区分在许多应用中自然样品中观察到的可变性。
{"title":"A workflow-optimized protocol for accelerated sample preparation and automated Sr separation from natural waters for 87Sr/86Sr determination†","authors":"Grace N. Manestar, Hilary M. K. Lewis, Alex McCoy-West, Nishen Naidoo, Stefan Makart, Ondrea Thompson and Brandon Mahan","doi":"10.1039/D5JA00086F","DOIUrl":"https://doi.org/10.1039/D5JA00086F","url":null,"abstract":"<p >Radiogenic strontium (<small><sup>87</sup></small>Sr/<small><sup>86</sup></small>Sr) is a powerful tool for characterizing and differentiating water reservoirs (among many other applications). The development and improvement of high-precision analytical platforms (namely MC-ICP-MS) has enhanced throughput for isotope ratio determination. However, analyte purification—needed to remove isobaric interferences—continues to occur largely <em>via</em> conventional manual gravity-driven ion exchange chromatography (hereafter: manual IEC), which generally cannot match instrument throughput. This has created a persistent throughput gap that encumbers use and proliferation, emphasizing the need for rapid separation of Sr, and of comprehensive, end-to-end high throughput workflows and analytical approaches that are fit-for-purpose. Here we have developed a workflow-optimized protocol for sample preparation and separation of Sr from natural water samples using both workflow-optimized manual IEC and automated high pressure ion chromatography (HPIC), for subsequent analysis <em>via</em> MC-ICP-MS. These methods have been designed to seamlessly integrate with common international practice for water sample collection. The automated HPIC technique accommodates introduction of water samples filtered with standard 0.45 μm membranes and acidified with ultra-high purity nitric acid (HNO<small><sub>3</sub></small>, to pH of 1–2, approximated as 0.09 mol per L HNO<small><sub>3</sub></small>). Filtered and acidified samples are directly introduced into the HPIC system where Sr is separated from other cations (namely Ca) and collected as an isolate in a specific volume of ultrapure water. Strontium isolates, with no further preparation (<em>e.g.</em> dry-down and reflux), are then directly acidified to 0.5 mol per L HNO<small><sub>3</sub></small> and analyzed by MC-ICP-MS. This technique can process 40–50 samples in a 24 hour period with mitigated potential for human error, matching current MC-ICP-MS analytical capacity, and achieving analytical precision sufficient to distinguish the variability observed in natural samples across many applications.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1666-1677"},"PeriodicalIF":3.1,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00086f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536818","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}
Doru Pacesila, Iuliana Stanciu, Razvan Gornea, William E. Kieser, Nimal De Silva, Albert Zondervan, Barbara Francisco, Michaela Froehlich, Michael Hotchkis, Marie-Cécile Piro and Guillaume Giroux
This study focuses on the precise quantification of 210Pb contamination in metallic copper, an essential construction material of ultra-sensitive detectors in astroparticle physics, by Accelerator Mass Spectrometry. For the most stable and durable anion beam current from the Cs sputter source, PbF2 in a mixture with fine Ag powder was found to be preferable over PbO + Ag. After tandem acceleration and electron stripping with helium, the maximum 206Pb3+ current was 0.11 μA, and the 210Pb detection efficiency was 1.3 × 10−4. Investigation of several methods to extract lead from copper, with HNO3, NH4OH, and H2SO4, led to chemical recovery rates up to 92%. Following the development of chemical and target preparation procedures, an upper limit of 210Pb = 62 mBq kg−1 was determined for the NEWS-G copper (Aurubis) sample, consistent with previous results obtained by α-spectrometry. Tests with copper plates exposed to an atmosphere of 222Rn (1625 Bq m−3) for 182 hours showed significant 210Pb surface contamination (0.56 ± 0.16 Bq m−2), underscoring the importance of minimizing radon in spaces where metallic copper is chemically and/or physically processed.
{"title":"Assay of lead-210 in metallic copper via accelerator mass spectrometry","authors":"Doru Pacesila, Iuliana Stanciu, Razvan Gornea, William E. Kieser, Nimal De Silva, Albert Zondervan, Barbara Francisco, Michaela Froehlich, Michael Hotchkis, Marie-Cécile Piro and Guillaume Giroux","doi":"10.1039/D5JA00105F","DOIUrl":"https://doi.org/10.1039/D5JA00105F","url":null,"abstract":"<p >This study focuses on the precise quantification of <small><sup>210</sup></small>Pb contamination in metallic copper, an essential construction material of ultra-sensitive detectors in astroparticle physics, by Accelerator Mass Spectrometry. For the most stable and durable anion beam current from the Cs sputter source, PbF<small><sub>2</sub></small> in a mixture with fine Ag powder was found to be preferable over PbO + Ag. After tandem acceleration and electron stripping with helium, the maximum <small><sup>206</sup></small>Pb<small><sup>3+</sup></small> current was 0.11 μA, and the <small><sup>210</sup></small>Pb detection efficiency was 1.3 × 10<small><sup>−4</sup></small>. Investigation of several methods to extract lead from copper, with HNO<small><sub>3</sub></small>, NH<small><sub>4</sub></small>OH, and H<small><sub>2</sub></small>SO<small><sub>4</sub></small>, led to chemical recovery rates up to 92%. Following the development of chemical and target preparation procedures, an upper limit of <small><sup>210</sup></small>Pb = 62 mBq kg<small><sup>−1</sup></small> was determined for the NEWS-G copper (Aurubis) sample, consistent with previous results obtained by α-spectrometry. Tests with copper plates exposed to an atmosphere of <small><sup>222</sup></small>Rn (1625 Bq m<small><sup>−3</sup></small>) for 182 hours showed significant <small><sup>210</sup></small>Pb surface contamination (0.56 ± 0.16 Bq m<small><sup>−2</sup></small>), underscoring the importance of minimizing radon in spaces where metallic copper is chemically and/or physically processed.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1852-1861"},"PeriodicalIF":3.1,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536748","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}
Abdallah A. Shaltout, Messaoud Harfouche, Omar H. Abd-Elkader and Diane Eichert
Correction for ‘The occurrence and sources of Ni in ambient air particulates using synchrotron radiation based X-ray fluorescence and X-ray absorption near edge structure’ by Abdallah A. Shaltout et al., J. Anal. At. Spectrom., 2025, 40, 1297–1308, https://doi.org/10.1039/D5JA00043B.
对“基于同步辐射的x射线荧光和x射线吸收近边结构的环境空气颗粒中Ni的发生和来源”的校正,作者:Abdallah A. shalout等人,J. Anal。在。范围。, 2025, 40, 1297-1308, https://doi.org/10.1039/D5JA00043B。
{"title":"Correction: The occurrence and sources of Ni in ambient air particulates using synchrotron radiation based X-ray fluorescence and X-ray absorption near edge structure","authors":"Abdallah A. Shaltout, Messaoud Harfouche, Omar H. Abd-Elkader and Diane Eichert","doi":"10.1039/D5JA90024G","DOIUrl":"https://doi.org/10.1039/D5JA90024G","url":null,"abstract":"<p >Correction for ‘The occurrence and sources of Ni in ambient air particulates using synchrotron radiation based X-ray fluorescence and X-ray absorption near edge structure’ by Abdallah A. Shaltout <em>et al., J. Anal. At. Spectrom.</em>, 2025, <strong>40</strong>, 1297–1308, https://doi.org/10.1039/D5JA00043B.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1862-1862"},"PeriodicalIF":3.1,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja90024g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536749","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}
Raven L. Buckman Johnson, Hark Karkee and Alexander Gundlach-Graham
Single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) can be used to measure metal-containing nanoparticles (NPs) and sub-micron particles (μPs) at environmentally relevant concentrations. Multielement fingerprints measured by spICP-TOFMS can also be used to differentiate natural and anthropogenic particle types. Thus, the approach offers a promising route to classify, quantify, and track anthropogenic NPs and μPs in natural systems. However, biases in spICP-TOFMS data caused by analytical sensitivities, Poisson detection statistics, and elemental variability at the single-particle level complicate particle-type classification. To overcome the inherent bias in spICP-TOFMS data for the classification of particle types, we have developed a multi-stage semi-supervised machine learning (SSML) strategy that identifies and subsequently trains on systematic noise in spICP-TOFMS data to produce more robust particle-type classifications. Here, we apply our two-stage SSML model to classify individual Ti-containing NPs and μPs via spICP-TOFMS analysis. To build our model, we measure neat suspensions of anthropogenic TiO2 particles (E171) and natural titanium-containing particle types: rutile, ilmenite, and biotite by spICP-TOFMS. Element mass amounts recorded per particle are used to classify particle type by SSML and then systematic particle misclassifications are identified and recorded as uncertainty classes. Following, a second SSML model is trained with the addition of uncertain particle-type categories. With two-stage SSML, we demonstrate low false-positive rates (≤5%) and moderate particle recoveries (50–90%) for all anthropogenic and natural particle types. Two-stage SSML is a streamlined, hands-off method to identify and overcome bias in spICP-TOFMS training data that provides a robust particle-type classification.
{"title":"Two-stage semi-supervised machine learning for classification of Ti-rich nanoparticles and microparticles measured by spICP-TOFMS†","authors":"Raven L. Buckman Johnson, Hark Karkee and Alexander Gundlach-Graham","doi":"10.1039/D5JA00108K","DOIUrl":"https://doi.org/10.1039/D5JA00108K","url":null,"abstract":"<p >Single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) can be used to measure metal-containing nanoparticles (NPs) and sub-micron particles (μPs) at environmentally relevant concentrations. Multielement fingerprints measured by spICP-TOFMS can also be used to differentiate natural and anthropogenic particle types. Thus, the approach offers a promising route to classify, quantify, and track anthropogenic NPs and μPs in natural systems. However, biases in spICP-TOFMS data caused by analytical sensitivities, Poisson detection statistics, and elemental variability at the single-particle level complicate particle-type classification. To overcome the inherent bias in spICP-TOFMS data for the classification of particle types, we have developed a multi-stage semi-supervised machine learning (SSML) strategy that identifies and subsequently trains on systematic noise in spICP-TOFMS data to produce more robust particle-type classifications. Here, we apply our two-stage SSML model to classify individual Ti-containing NPs and μPs <em>via</em> spICP-TOFMS analysis. To build our model, we measure neat suspensions of anthropogenic TiO<small><sub>2</sub></small> particles (E171) and natural titanium-containing particle types: rutile, ilmenite, and biotite by spICP-TOFMS. Element mass amounts recorded per particle are used to classify particle type by SSML and then systematic particle misclassifications are identified and recorded as uncertainty classes. Following, a second SSML model is trained with the addition of uncertain particle-type categories. With two-stage SSML, we demonstrate low false-positive rates (≤5%) and moderate particle recoveries (50–90%) for all anthropogenic and natural particle types. Two-stage SSML is a streamlined, hands-off method to identify and overcome bias in spICP-TOFMS training data that provides a robust particle-type classification.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1658-1665"},"PeriodicalIF":3.1,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00108k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536817","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}
Li-Guang Wu, Xiao-Xiao Ling, Guo-Qiang Tang, Yu Liu, Zhenyu Chen, Qiu-Li Li, Xian-Hua Li and Benita Putlitz
Xenotime is a common accessory mineral found in igneous, metamorphic, and sedimentary rocks, as well as hydrothermal ore deposits. Although the U–Th–Pb isotopic compositions of xenotime have been used widely to constrain host rock ages, O isotopic compositions have rarely been exploited. A major challenge is that microanalysis techniques, such as secondary ion mass spectrometry (SIMS), are required to analyze small and zoned xenotime crystals, and these techniques require matrix-matched reference materials to correct for instrumental mass fractionation and to monitor analytical accuracy. Currently, there are no reference materials for SIMS O isotopic analysis of xenotime, which impedes its application in geological studies. We present PX xenotime, a sample collected from Zagi Mountain, Pakistan, that exhibits a homogeneous O isotopic composition as confirmed through SIMS analyses. Laser fluorination–isotopic ratio mass spectrometry yielded a δ18O value of 6.25‰ ± 0.13‰ (2SD, n = 6). Thus, we establish PX xenotime as the first reference material for SIMS xenotime O isotopic analysis. We also explore the potential applications of SIMS xenotime O isotopic analysis through O isotopic fractionation between quartz and xenotime and between xenotime and water. Our results show that the quartz–xenotime O isotope thermometer is promising for low-temperature hydrothermal systems (<400 °C). Moreover, fluid δ18O compositions can be directly determined by SIMS quartz–xenotime δ18O analysis in a single session.
{"title":"PX xenotime: a new reference material for SIMS oxygen isotopic microanalysis and potential applications†","authors":"Li-Guang Wu, Xiao-Xiao Ling, Guo-Qiang Tang, Yu Liu, Zhenyu Chen, Qiu-Li Li, Xian-Hua Li and Benita Putlitz","doi":"10.1039/D5JA00006H","DOIUrl":"https://doi.org/10.1039/D5JA00006H","url":null,"abstract":"<p >Xenotime is a common accessory mineral found in igneous, metamorphic, and sedimentary rocks, as well as hydrothermal ore deposits. Although the U–Th–Pb isotopic compositions of xenotime have been used widely to constrain host rock ages, O isotopic compositions have rarely been exploited. A major challenge is that microanalysis techniques, such as secondary ion mass spectrometry (SIMS), are required to analyze small and zoned xenotime crystals, and these techniques require matrix-matched reference materials to correct for instrumental mass fractionation and to monitor analytical accuracy. Currently, there are no reference materials for SIMS O isotopic analysis of xenotime, which impedes its application in geological studies. We present PX xenotime, a sample collected from Zagi Mountain, Pakistan, that exhibits a homogeneous O isotopic composition as confirmed through SIMS analyses. Laser fluorination–isotopic ratio mass spectrometry yielded a <em>δ</em><small><sup>18</sup></small>O value of 6.25‰ ± 0.13‰ (2SD, <em>n</em> = 6). Thus, we establish PX xenotime as the first reference material for SIMS xenotime O isotopic analysis. We also explore the potential applications of SIMS xenotime O isotopic analysis through O isotopic fractionation between quartz and xenotime and between xenotime and water. Our results show that the quartz–xenotime O isotope thermometer is promising for low-temperature hydrothermal systems (<400 °C). Moreover, fluid <em>δ</em><small><sup>18</sup></small>O compositions can be directly determined by SIMS quartz–xenotime <em>δ</em><small><sup>18</sup></small>O analysis in a single session.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1788-1795"},"PeriodicalIF":3.1,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536741","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}
We present a novel method for measurement of 207Pb/206Pb and 208Pb/206Pb isotope ratios in solid samples, employing vacuum ultraviolet (VUV) laser ablation/ionization coupled with a time-of-flight reflectron mass spectrometer (VUV-TOF). The 125.5 nm VUV laser, generated via four-wave mixing in an Hg cell driven by a YAG-pumped two-dye laser system, offers a simpler and more robust alternative to previous configurations. Advanced data collection and processing protocols enable calibration-free Pb isotope ratio measurements with accuracies better than 1.6% (2 times the relative standard deviations) for reference materials NIST 610, NIST 612 and zircon FC1. Notably, isotope ratios remain stable despite variations in Pb+ signal intensities caused by downhole fractionation. Semi-quantitative trace element sensitivities, determined using NIST 610, further highlight the method's versatility. With an ablation spot size smaller than 2 μm, this technique is ideally suited for high-spatial-resolution applications, including the dating of zoned zircons. The combination of precision, sensitivity, and robustness establishes VUV-TOF mass spectrometry as a powerful tool for advancing isotopic analysis in geochronology and geochemistry.
{"title":"Pb isotope ratio and trace element analysis using VUV-TOF mass spectrometry: applications to NIST 610/612 and zircon FC1†","authors":"Yixuan Li, Haoyu Shi, Peng Wang and Yuxiang Mo","doi":"10.1039/D5JA00142K","DOIUrl":"https://doi.org/10.1039/D5JA00142K","url":null,"abstract":"<p >We present a novel method for measurement of <small><sup>207</sup></small>Pb/<small><sup>206</sup></small>Pb and <small><sup>208</sup></small>Pb/<small><sup>206</sup></small>Pb isotope ratios in solid samples, employing vacuum ultraviolet (VUV) laser ablation/ionization coupled with a time-of-flight reflectron mass spectrometer (VUV-TOF). The 125.5 nm VUV laser, generated <em>via</em> four-wave mixing in an Hg cell driven by a YAG-pumped two-dye laser system, offers a simpler and more robust alternative to previous configurations. Advanced data collection and processing protocols enable calibration-free Pb isotope ratio measurements with accuracies better than 1.6% (2 times the relative standard deviations) for reference materials NIST 610, NIST 612 and zircon FC1. Notably, isotope ratios remain stable despite variations in Pb<small><sup>+</sup></small> signal intensities caused by downhole fractionation. Semi-quantitative trace element sensitivities, determined using NIST 610, further highlight the method's versatility. With an ablation spot size smaller than 2 μm, this technique is ideally suited for high-spatial-resolution applications, including the dating of zoned zircons. The combination of precision, sensitivity, and robustness establishes VUV-TOF mass spectrometry as a powerful tool for advancing isotopic analysis in geochronology and geochemistry.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1833-1844"},"PeriodicalIF":3.1,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536746","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}
Robert Clough, Chris F. Harrington, Steve J. Hill, Yolanda Madrid and Julian F. Tyson
This is the 17th Atomic Spectrometry Update (ASU) to focus on advances in elemental speciation and covers a period of approximately 12 months from January 2024. This ASU review deals with all aspects of analytical atomic spectrometry speciation methods developed for: the determination of oxidation states; organometallic compounds; coordination compounds; metal and heteroatom-containing biomolecules, including metalloproteins, proteins, peptides and amino acids; and the use of metal-tagging to facilitate detection via atomic spectrometry. As with all ASU reviews, the focus of the research reviewed includes those methods that incorporate atomic spectrometry as the measurement technique, although molecular detection techniques are also included where they have provided a complementary approach to speciation analysis. The number of publications covered this year has increased since last year but remains relatively low compared to many of the years that this ASU has been published for. However, there is a good breadth of elements covered, with the most popular elements still being As, Hg and Se, although there is little novelty in the analytical approaches employed, which reflects the maturity of elemental speciation analysis, and over 25 elements are covered in total, including a growing number of papers covering essential macro and trace elements, such as Fe and Mn and P, and S as a heteroatom in proteins. The advent of ICP-MS/MS instrumentation, allowing for the cost-effective quantification of S as SO at m/z 48, thus negating the 16O2 interference is probably behind the rise in papers on this element once again, the quality of the abstract for many of the papers is poor, with details on the methodology, key results with data included, conclusions and implications thereof missing. This is likely to lead to fewer researchers reading the article or considering it for reviews such as those produced by the ASU.
{"title":"Atomic spectrometry update: review of advances in elemental speciation","authors":"Robert Clough, Chris F. Harrington, Steve J. Hill, Yolanda Madrid and Julian F. Tyson","doi":"10.1039/D5JA90023A","DOIUrl":"https://doi.org/10.1039/D5JA90023A","url":null,"abstract":"<p >This is the 17th Atomic Spectrometry Update (ASU) to focus on advances in elemental speciation and covers a period of approximately 12 months from January 2024. This ASU review deals with all aspects of analytical atomic spectrometry speciation methods developed for: the determination of oxidation states; organometallic compounds; coordination compounds; metal and heteroatom-containing biomolecules, including metalloproteins, proteins, peptides and amino acids; and the use of metal-tagging to facilitate detection <em>via</em> atomic spectrometry. As with all ASU reviews, the focus of the research reviewed includes those methods that incorporate atomic spectrometry as the measurement technique, although molecular detection techniques are also included where they have provided a complementary approach to speciation analysis. The number of publications covered this year has increased since last year but remains relatively low compared to many of the years that this ASU has been published for. However, there is a good breadth of elements covered, with the most popular elements still being As, Hg and Se, although there is little novelty in the analytical approaches employed, which reflects the maturity of elemental speciation analysis, and over 25 elements are covered in total, including a growing number of papers covering essential macro and trace elements, such as Fe and Mn and P, and S as a heteroatom in proteins. The advent of ICP-MS/MS instrumentation, allowing for the cost-effective quantification of S as SO at <em>m</em>/<em>z</em> 48, thus negating the <small><sup>16</sup></small>O<small><sub>2</sub></small> interference is probably behind the rise in papers on this element once again, the quality of the abstract for many of the papers is poor, with details on the methodology, key results with data included, conclusions and implications thereof missing. This is likely to lead to fewer researchers reading the article or considering it for reviews such as those produced by the ASU.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1615-1644"},"PeriodicalIF":3.1,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536814","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}
Ahmed A. AL-Tameemi, Fusheng Li, Qinglun Zhang, Zenan Xiao, Wanqi Yang and Shubin Lyu
Precise determination of heavy metal element concentrations in ores is vital for sustainable resource utilization, environmental protection, and industrial applications. X-ray fluorescence spectroscopy (XRF) has emerged as a preferred technique owing to its non-destructive, rapid, and on-site analytical capabilities. However, challenges such as matrix effects, spectral line interference, and instrumental noise often limit its accuracy. In this paper, a novel deep learning model, the Hierarchical Convolutional Network with Attention Excitation (HCNAE) is developed to enhance the prediction of heavy metal element quantification, copper (Cu), zinc (Zn), and lead (Pb), in ores using XRF spectra. First, ore spectra were acquired using a handheld XRF analyzer. Second, to address challenges such as spectral continuity, inter-channel correlations, and matrix effects, a HCNAE was developed. The HCNAE model incorporates hierarchical convolutional layers for global and local feature extraction and a squeeze-and-excitation (SE) mechanism for dynamic channel recalibration. Finally, the model integrates feature extraction, attention mechanisms, and regression tasks in an end-to-end framework, enabling the accurate concentration estimation of heavy metal elements. The performance of the model was compared with six widely used machine learning and deep learning algorithms to ensure a comprehensive evaluation. The HCNAE achieved coefficients of determination of 0.9961, 0.9715, and 0.9894 for Cu, Zn, and Pb, respectively. The results demonstrate the effectiveness of the HCNAE in mitigating matrix effects and spectral interference in XRF, offering accurate predictions even under challenging conditions. This study presents HCNAE as a scalable and innovative solution for heavy metal element quantification in ores, providing a strong foundation for advancements in mining and geological research.
{"title":"Quantitative analysis of Cu, Zn, and Pb elements in ores by X-ray fluorescence using a hierarchical convolutional network with attention excitation","authors":"Ahmed A. AL-Tameemi, Fusheng Li, Qinglun Zhang, Zenan Xiao, Wanqi Yang and Shubin Lyu","doi":"10.1039/D5JA00047E","DOIUrl":"https://doi.org/10.1039/D5JA00047E","url":null,"abstract":"<p >Precise determination of heavy metal element concentrations in ores is vital for sustainable resource utilization, environmental protection, and industrial applications. X-ray fluorescence spectroscopy (XRF) has emerged as a preferred technique owing to its non-destructive, rapid, and on-site analytical capabilities. However, challenges such as matrix effects, spectral line interference, and instrumental noise often limit its accuracy. In this paper, a novel deep learning model, the Hierarchical Convolutional Network with Attention Excitation (HCNAE) is developed to enhance the prediction of heavy metal element quantification, copper (Cu), zinc (Zn), and lead (Pb), in ores using XRF spectra. First, ore spectra were acquired using a handheld XRF analyzer. Second, to address challenges such as spectral continuity, inter-channel correlations, and matrix effects, a HCNAE was developed. The HCNAE model incorporates hierarchical convolutional layers for global and local feature extraction and a squeeze-and-excitation (SE) mechanism for dynamic channel recalibration. Finally, the model integrates feature extraction, attention mechanisms, and regression tasks in an end-to-end framework, enabling the accurate concentration estimation of heavy metal elements. The performance of the model was compared with six widely used machine learning and deep learning algorithms to ensure a comprehensive evaluation. The HCNAE achieved coefficients of determination of 0.9961, 0.9715, and 0.9894 for Cu, Zn, and Pb, respectively. The results demonstrate the effectiveness of the HCNAE in mitigating matrix effects and spectral interference in XRF, offering accurate predictions even under challenging conditions. This study presents HCNAE as a scalable and innovative solution for heavy metal element quantification in ores, providing a strong foundation for advancements in mining and geological research.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 6","pages":" 1580-1590"},"PeriodicalIF":3.1,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144213681","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}
Claire A. Richards, Matthew A. Turner and Amy J. Managh
Optimal sampler and skimmer cone orifice diameter has been well developed for solution based inductively coupled plasma-mass spectrometry (ICP-MS) but is not fully understood for modern laser ablation (LA) systems. This research investigates the impact of various cone orifice sets and the effect they have on ICP-MS sensitivity using solution mode and whilst using a low-dispersion LA system. A wide range of elements between the masses 7Li and 238U and their oxides have been measured via solution nebulisation as well as NIST 610 glass reference material and multi-elemental gelatine microdroplets via laser ablation. For multi-elemental micro droplets, 7 out of 11 elements analysed showed a statistically significant increase in sensitivity when a reduction of cone orifice size of 0.1 mm was used, compared to the standard cone orifice size. Similarly, for the ablation of NIST 610, 7 out of 11 elements displayed a statistically higher sensitivity with a 0.1 mm reduced orifice size. This analysis has confirmed suitability of standard cone sets for nebulisation of homogeneous solutions whilst suggesting a slight reduction in cone orifice diameter improves ion transmission through the cones towards the mass spectrometer by up to 272% (NIST 610) or 124% (multi-elemental droplets) for LA-ICP-MS.
{"title":"The influence of cone orifice diameter on ion transmission in solution and laser ablation ICP-MS†","authors":"Claire A. Richards, Matthew A. Turner and Amy J. Managh","doi":"10.1039/D5JA00046G","DOIUrl":"https://doi.org/10.1039/D5JA00046G","url":null,"abstract":"<p >Optimal sampler and skimmer cone orifice diameter has been well developed for solution based inductively coupled plasma-mass spectrometry (ICP-MS) but is not fully understood for modern laser ablation (LA) systems. This research investigates the impact of various cone orifice sets and the effect they have on ICP-MS sensitivity using solution mode and whilst using a low-dispersion LA system. A wide range of elements between the masses <small><sup>7</sup></small>Li and <small><sup>238</sup></small>U and their oxides have been measured <em>via</em> solution nebulisation as well as NIST 610 glass reference material and multi-elemental gelatine microdroplets <em>via</em> laser ablation. For multi-elemental micro droplets, 7 out of 11 elements analysed showed a statistically significant increase in sensitivity when a reduction of cone orifice size of 0.1 mm was used, compared to the standard cone orifice size. Similarly, for the ablation of NIST 610, 7 out of 11 elements displayed a statistically higher sensitivity with a 0.1 mm reduced orifice size. This analysis has confirmed suitability of standard cone sets for nebulisation of homogeneous solutions whilst suggesting a slight reduction in cone orifice diameter improves ion transmission through the cones towards the mass spectrometer by up to 272% (NIST 610) or 124% (multi-elemental droplets) for LA-ICP-MS.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1726-1732"},"PeriodicalIF":3.1,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d5ja00046g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536713","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}
Lan-Lan Tian, Xiao-Lei Wang, Yue Guan, Wen-Li Xie, Kexin Xu, Feng-Tai Tong, Tao Yang and Yong-Bo Peng
Barite serves as a crucial archive for reconstructing sulfur cycling evolution throughout geologic history. Microscale space variations in sulfur isotope compositions (δ34S) of barite provide valuable insights into the barite precipitation process. While secondary ion mass spectrometry (SIMS) microanalysis has emerged as a powerful tool for such investigations, the availability of high quality reference materials remains a fundamental requirement for accurate measurements. Although several barite reference materials have been developed for SIMS analysis, the potential influence of crystallographic orientation on sulfur isotope measurements has not been systematically evaluated. Moreover, the development of more in situ barite reference materials with diverse sulfur isotopic compositions would greatly facilitate cross-laboratory data comparison. In this study, we conducted a comprehensive investigation of the crystallographic orientation effect by combining electron backscatter diffraction (EBSD) and SIMS analyses. Our results demonstrate that crystallographic orientation does not produce significant analytical bias in SIMS barite sulfur isotope measurements at current levels of analytical precision. Furthermore, we present two new well-characterized potential reference materials NJU-Ba-1 and NJU-Ba-2 barite specifically developed for microbeam sulfur isotope analysis. Detailed characterization of texture and major element composition confirms the absence of internal zoning in ground fragments from both barite specimens. These two reference materials establish an extended δ34SV-CDT calibration range for microanalytical studies, with certified values of 6.18 ± 0.34‰ (2SD, N = 17) and 14.16 ± 0.26‰ (2SD, N = 9) for NJU-Ba-1 and NJU-Ba-2 respectively, as determined by gas-source isotope ratio mass spectrometry (GS-IRMS). Extensive SIMS analyses revealed exceptional homogeneity at both inter- and intra-unit scales, with δ34S variations of 0.36‰ (2SD, N = 328) for NJU-Ba-1 and 0.45‰ (2SD, N = 343) for NJU-Ba-2. These performance characteristics indicate that NJU-Ba-1 and NJU-Ba-2 are promising candidates as reference materials for high-precision microanalytical studies of barite sulfur isotopes.
重晶石是重建整个地质历史中硫循环演化的重要档案。重晶石硫同位素组成(δ34S)的微尺度空间变化为研究重晶石沉淀过程提供了有价值的信息。虽然次级离子质谱(SIMS)微分析已成为此类研究的有力工具,但高质量参考物质的可用性仍然是准确测量的基本要求。虽然已经开发了几种用于SIMS分析的重晶石参考物质,但晶体取向对硫同位素测量的潜在影响尚未得到系统评估。此外,开发更多具有不同硫同位素组成的原位重晶石标准物质将极大地促进跨实验室数据的比较。在这项研究中,我们结合电子背散射衍射(EBSD)和SIMS分析对晶体取向效应进行了全面的研究。我们的研究结果表明,在当前的分析精度水平下,晶体取向在SIMS重晶石硫同位素测量中不会产生显著的分析偏差。此外,我们提出了两种新的具有良好表征的潜在参考物质NJU-Ba-1和NJU-Ba-2重晶石,专门用于微束硫同位素分析。纹理和主要元素组成的详细表征证实了两个重晶石标本的地面碎片中没有内部分带。采用气源同位素质谱法(GS-IRMS)测定NJU-Ba-1和NJU-Ba-2的δ34SV-CDT标准值分别为6.18±0.34‰(2SD, N = 17)和14.16±0.26‰(2SD, N = 9),建立了扩展的δ34SV-CDT标准范围。广泛的SIMS分析显示,NJU-Ba-1和NJU-Ba-2的δ34S变化幅度分别为0.36‰(2SD, N = 328)和0.45‰(2SD, N = 343)。这些性能特征表明NJU-Ba-1和NJU-Ba-2是重晶石硫同位素高精度微量分析研究的理想参考物质。
{"title":"Two new barite reference materials for SIMS sulfur isotope analysis: evaluation of the crystallographic orientation effect and homogeneity†","authors":"Lan-Lan Tian, Xiao-Lei Wang, Yue Guan, Wen-Li Xie, Kexin Xu, Feng-Tai Tong, Tao Yang and Yong-Bo Peng","doi":"10.1039/D5JA00123D","DOIUrl":"https://doi.org/10.1039/D5JA00123D","url":null,"abstract":"<p >Barite serves as a crucial archive for reconstructing sulfur cycling evolution throughout geologic history. Microscale space variations in sulfur isotope compositions (<em>δ</em><small><sup>34</sup></small>S) of barite provide valuable insights into the barite precipitation process. While secondary ion mass spectrometry (SIMS) microanalysis has emerged as a powerful tool for such investigations, the availability of high quality reference materials remains a fundamental requirement for accurate measurements. Although several barite reference materials have been developed for SIMS analysis, the potential influence of crystallographic orientation on sulfur isotope measurements has not been systematically evaluated. Moreover, the development of more <em>in situ</em> barite reference materials with diverse sulfur isotopic compositions would greatly facilitate cross-laboratory data comparison. In this study, we conducted a comprehensive investigation of the crystallographic orientation effect by combining electron backscatter diffraction (EBSD) and SIMS analyses. Our results demonstrate that crystallographic orientation does not produce significant analytical bias in SIMS barite sulfur isotope measurements at current levels of analytical precision. Furthermore, we present two new well-characterized potential reference materials NJU-Ba-1 and NJU-Ba-2 barite specifically developed for microbeam sulfur isotope analysis. Detailed characterization of texture and major element composition confirms the absence of internal zoning in ground fragments from both barite specimens. These two reference materials establish an extended <em>δ</em><small><sup>34</sup></small>S<small><sub>V-CDT</sub></small> calibration range for microanalytical studies, with certified values of 6.18 ± 0.34‰ (2SD, <em>N</em> = 17) and 14.16 ± 0.26‰ (2SD, <em>N</em> = 9) for NJU-Ba-1 and NJU-Ba-2 respectively, as determined by gas-source isotope ratio mass spectrometry (GS-IRMS). Extensive SIMS analyses revealed exceptional homogeneity at both inter- and intra-unit scales, with <em>δ</em><small><sup>34</sup></small>S variations of 0.36‰ (2SD, <em>N</em> = 328) for NJU-Ba-1 and 0.45‰ (2SD, <em>N</em> = 343) for NJU-Ba-2. These performance characteristics indicate that NJU-Ba-1 and NJU-Ba-2 are promising candidates as reference materials for high-precision microanalytical studies of barite sulfur isotopes.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 7","pages":" 1845-1851"},"PeriodicalIF":3.1,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144536747","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}