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A workflow-optimized protocol for accelerated sample preparation and automated Sr separation from natural waters for 87Sr/86Sr determination† 一种工作流程优化的方案,用于加速样品制备和自动从自然水中分离锶,用于87Sr/86Sr测定†
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-06-06 DOI: 10.1039/D5JA00086F
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。
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引用次数: 0
Assay of lead-210 in metallic copper via accelerator mass spectrometry 用加速器质谱法测定金属铜中的铅210
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-06-04 DOI: 10.1039/D5JA00105F
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.

本研究利用加速器质谱法对天体粒子物理超灵敏探测器必不可少的材料金属铜中的210Pb污染进行了精确定量分析。对于Cs溅射源的最稳定和持久的阴离子束电流,发现PbF2与细银粉的混合物比PbO + Ag更好。经氦串联加速和电子剥离后,206Pb3+的最大电流为0.11 μA, 210Pb的检测效率为1.3 × 10−4。采用HNO3、NH4OH、H2SO4三种萃取方法从铜中提取铅,化学回收率高达92%。根据化学和靶制备工艺的发展,确定了NEWS-G铜(Aurubis)样品的上限为210Pb = 62 mBq kg−1,与先前的α-光谱分析结果一致。将铜板暴露在222Rn (1625 Bq m−3)大气中182小时的测试显示,表面有明显的210Pb污染(0.56±0.16 Bq m−2),强调了在对金属铜进行化学和/或物理处理的空间中尽量减少氡的重要性。
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引用次数: 0
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 校正:利用基于同步辐射的x射线荧光和x射线吸收近边结构研究环境空气颗粒物中Ni的存在和来源
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-06-02 DOI: 10.1039/D5JA90024G
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。
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引用次数: 0
Two-stage semi-supervised machine learning for classification of Ti-rich nanoparticles and microparticles measured by spICP-TOFMS† spICP-TOFMS测量的富钛纳米粒子和微粒子的两阶段半监督机器学习分类
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-31 DOI: 10.1039/D5JA00108K
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.

单粒子电感耦合等离子体飞行时间质谱法(spICP-TOFMS)可以测量环境相关浓度下的含金属纳米粒子(NPs)和亚微米粒子(μPs)。用spICP-TOFMS测定的多元素指纹图谱也可用于区分自然和人为颗粒类型。因此,该方法为分类、量化和跟踪自然系统中人为NPs和μPs提供了一条有前途的途径。然而,spICP-TOFMS数据中由分析灵敏度、泊松检测统计量和单粒子水平的元素变异引起的偏差使粒子类型分类复杂化。为了克服spICP-TOFMS数据在粒子类型分类方面的固有偏差,我们开发了一种多阶段半监督机器学习(SSML)策略,该策略可以识别spICP-TOFMS数据中的系统噪声并随后对其进行训练,以产生更鲁棒的粒子类型分类。本文采用两阶段SSML模型,通过spICP-TOFMS分析对单个含ti的NPs和μPs进行分类。为了建立我们的模型,我们用spICP-TOFMS测量了人为二氧化钛颗粒(E171)和天然含钛颗粒类型:金红石、钛铁矿和黑云母的纯悬浮。利用SSML记录的每个粒子的元素质量量来划分粒子类型,然后识别出系统的粒子错误分类并记录为不确定等级。接下来,用不确定粒子类型类别的加入训练第二个SSML模型。对于所有人为和自然颗粒类型,我们证明了低假阳性率(≤5%)和中等颗粒回收率(50-90%)的两阶段SSML。两阶段SSML是一种简化的、不干涉的方法,用于识别和克服spICP-TOFMS训练数据中的偏差,提供了稳健的粒子类型分类。
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引用次数: 0
PX xenotime: a new reference material for SIMS oxygen isotopic microanalysis and potential applications† PX xenotime:一种新的SIMS氧同位素微量分析参考物质及其潜在应用
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-30 DOI: 10.1039/D5JA00006H
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.

Xenotime是一种常见的辅助矿物,存在于火成岩、变质岩和沉积岩以及热液矿床中。虽然xenotime的U-Th-Pb同位素组成已被广泛用于约束寄主岩石年龄,但O同位素组成很少被利用。一个主要的挑战是微分析技术,如二次离子质谱(SIMS),需要分析小的和带状的xenotime晶体,这些技术需要基质匹配的参考物质来校正仪器质量分馏和监测分析精度。目前,xenotime的SIMS O同位素分析缺乏参考材料,阻碍了其在地质研究中的应用。我们提出的PX xenotime样品采集自巴基斯坦Zagi山,通过SIMS分析证实其O同位素组成均匀。激光氟化-同位素比值质谱测定的δ18O值为6.25‰±0.13‰(2SD, n = 6)。因此,我们建立了PX xenotime作为SIMS xenotime O同位素分析的第一参考物质。我们还通过石英与xenotime之间以及xenotime与水之间的O同位素分馏,探索了SIMS xenotime O同位素分析的潜在应用。我们的结果表明,石英- xenotime O同位素温度计在低温热液系统(<400°C)中是有希望的。此外,SIMS石英- xenotime δ18O单次分析可直接确定流体的δ18O组成。
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引用次数: 0
Pb isotope ratio and trace element analysis using VUV-TOF mass spectrometry: applications to NIST 610/612 and zircon FC1† 使用vv - tof质谱分析Pb同位素比率和微量元素:应用于NIST 610/612和锆石FC1†
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-30 DOI: 10.1039/D5JA00142K
Yixuan Li, Haoyu Shi, Peng Wang and Yuxiang Mo

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.

本文提出了一种利用真空紫外(VUV)激光烧蚀/电离耦合飞行时间反射质谱计(VUV- tof)测量固体样品中207Pb/206Pb和208Pb/206Pb同位素比值的新方法。125.5 nm VUV激光器由yag泵浦双染料激光系统驱动,通过汞电池中的四波混频产生,比以前的配置提供了更简单、更强大的选择。先进的数据收集和处理方案使参考物质NIST 610, NIST 612和锆石FC1的无需校准的Pb同位素比测量精度优于1.6%(相对标准偏差的2倍)。值得注意的是,尽管井下分馏引起Pb+信号强度的变化,同位素比率仍然保持稳定。使用NIST 610测定的半定量微量元素灵敏度进一步突出了该方法的多功能性。该技术的烧蚀点尺寸小于2 μm,非常适合用于高空间分辨率的应用,包括分带锆石的测年。VUV-TOF质谱法结合了精度、灵敏度和稳健性,使其成为推进地球年代学和地球化学同位素分析的有力工具。
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引用次数: 0
Atomic spectrometry update: review of advances in elemental speciation 原子光谱法最新进展:元素物种形成的进展综述
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-27 DOI: 10.1039/D5JA90023A
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.

这是第17次原子光谱更新(ASU),重点关注元素物种形成的进展,涵盖了从2024年1月开始的大约12个月。这篇ASU回顾了原子光谱分析方法的所有方面:氧化态的测定;有机金属化合物;协调化合物;含金属和杂原子的生物分子,包括金属蛋白、蛋白质、多肽和氨基酸;并使用金属标记,以方便通过原子光谱检测。与所有亚利桑那州立大学的综述一样,研究综述的重点包括那些将原子光谱法作为测量技术的方法,尽管分子检测技术也包括在它们为物种形成分析提供补充方法的地方。自去年以来,今年所涵盖的出版物数量有所增加,但与该亚利桑那州立大学出版的许多年相比,仍然相对较低。然而,所涵盖的元素范围很广,最受欢迎的元素仍然是As、Hg和Se,尽管所采用的分析方法几乎没有新意,这反映了元素形态分析的成熟度,总共涵盖了超过25种元素,包括越来越多的论文涵盖了必需的宏量元素和微量元素,如Fe、Mn和P,以及作为蛋白质杂原子的S。ICP-MS/MS仪器的出现,允许在m/z 48下具有成本效益地定量S作为SO,从而否定16O2干扰,可能是关于这一元素的论文增加的背后,再一次,许多论文的摘要质量很差,关于方法的细节,包括数据的关键结果,结论及其含义缺失。这可能会导致更少的研究人员阅读这篇文章,或者考虑将其纳入ASU发表的评论中。
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引用次数: 0
Quantitative analysis of Cu, Zn, and Pb elements in ores by X-ray fluorescence using a hierarchical convolutional network with attention excitation 基于层次卷积神经网络的x射线荧光定量分析矿石中的Cu、Zn和Pb元素
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-23 DOI: 10.1039/D5JA00047E
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.

矿石中重金属元素浓度的精确测定对资源可持续利用、环境保护和工业应用具有重要意义。x射线荧光光谱(XRF)因其无损、快速和现场分析能力而成为首选技术。然而,诸如矩阵效应、谱线干扰和仪器噪声等挑战往往限制了其精度。本文提出了一种新的深度学习模型——带注意激励的层次卷积网络(HCNAE),以增强XRF光谱对矿石中铜(Cu)、锌(Zn)和铅(Pb)重金属元素定量的预测。首先,使用手持式XRF分析仪获取矿石光谱。其次,为了解决频谱连续性、信道间相关性和矩阵效应等挑战,开发了HCNAE。HCNAE模型结合了用于全局和局部特征提取的分层卷积层和用于动态通道重新校准的挤压和激励(SE)机制。最后,该模型将特征提取、注意机制和回归任务集成在一个端到端框架中,实现了重金属元素浓度的准确估计。将该模型的性能与六种广泛使用的机器学习和深度学习算法进行比较,以确保对其进行全面评估。HCNAE对Cu、Zn、Pb的测定系数分别为0.9961、0.9715、0.9894。结果证明了HCNAE在减轻XRF中的矩阵效应和光谱干扰方面的有效性,即使在具有挑战性的条件下也能提供准确的预测。该研究表明,HCNAE是一种可扩展的、创新的矿石重金属元素定量解决方案,为采矿和地质研究的进步提供了坚实的基础。
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引用次数: 0
The influence of cone orifice diameter on ion transmission in solution and laser ablation ICP-MS† 锥孔直径对离子在溶液中透射及激光烧蚀的影响
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-22 DOI: 10.1039/D5JA00046G
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.

对于基于溶液的电感耦合等离子体质谱(ICP-MS),最佳进样器和掠光器锥孔直径已经得到了很好的开发,但对于现代激光烧蚀(LA)系统,尚未完全了解。本研究使用溶液模式和低色散LA系统,研究了不同锥孔组的影响及其对ICP-MS灵敏度的影响。通过溶液雾化测量了7Li和238U之间的各种元素及其氧化物,并通过激光烧蚀测量了NIST 610玻璃基准材料和多元素明胶微滴。对于多元素微滴,当锥孔尺寸减小0.1 mm时,与标准锥孔尺寸相比,分析的11个元素中有7个显示出统计学上显著的灵敏度增加。同样,对于NIST 610的消融,当孔尺寸减小0.1 mm时,11个元件中有7个显示出统计上更高的灵敏度。该分析证实了标准锥套对均匀溶液雾化的适用性,同时表明锥孔直径的轻微减小可提高离子通过锥套向质谱仪的透射率,最高可达272% (NIST 610)或124%(多元素液滴),用于LA-ICP-MS。
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引用次数: 0
Two new barite reference materials for SIMS sulfur isotope analysis: evaluation of the crystallographic orientation effect and homogeneity† 用于SIMS硫同位素分析的两种新的重晶石基准物质:晶体取向效应和均匀性的评价
IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2025-05-22 DOI: 10.1039/D5JA00123D
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。
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引用次数: 0
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Journal of Analytical Atomic Spectrometry
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