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GEOSTANDARDS AND GEOANALYTICAL RESEARCH · 2024 · IF 2.7

Tourmaline Megacryst Reference Materials for High Precision In Situ Boron Isotope and Elemental Measurement by LA-MC-ICP-MS

Xiuhong Liao,Tao Chen,Tao Luo,Yue Cai,Wen Zhang,Zuowei Yin,Zhaochu Hu

Tourmaline serves as a vital recorder of geological processes. However, suitable tourmaline reference materials (RMs) for elemental and stable isotopic composition in situ measurements are still limited. In this study, three tourmaline megacrysts (MD-B66, IM-B232 and BR-DG68) were characterised as potential RMs for B isotope measurements by LA-MC-ICP-MS and mass fraction determinations by LA-ICP-MS. Over 251 measurements with LA-MC-ICP-MS on ten randomly selected fragments from MD-B66 consistently yielded B isotope ratios of -7.74 ± 0.25‰ (2 s ), establishing MD-B66 as a suitably homogeneous primary reference material for high-precision, in situ microbeam B isotope measurements. Notably, the (long-term) intermediate precision of 0.25‰ (2 s ) for in situ B isotope measurements obtained using this reference material is comparable to that reported from solution MC-ICP-MS methods in the literature. Two other tourmaline megacrysts, with intermediate precision ranging from ± 0.48‰ to ± 0.61‰ (2 s ) for δ 11 B measurement, can be employed as secondary RMs for quality control. The mean δ 11 B values determined by solution MC-ICP-MS for MD-B66 (-7.71 ± 0.32‰, n = 12), IM-B232 (-13.17 ± 0.62‰, n = 8) and BR-DG68 (-13.85 ± 0.32‰, n = 12), with expanded uncertainties at the 95% confidence level, are consistent with those determined by LA-MC-ICP-MS. Among these three new RMs, BR-DG68 displays relatively homogeneous major and trace element mass fractions. Characterisation using both in situ and wet chemical techniques demonstrated the suitability of BR-DG68 as the first tourmaline reference material for elemental measurement by LA-ICP-MS, which would permit matrix-matched and therefore more accurate elemental measurement in tourmalines. Unlike electron probe microanalysis with B and Li contents calculated based on stoichiometric assumptions, direct and accurate measurements of the two low atomic number elements, along with other major and trace elements can be achieved by LA-ICP-MS with the aid of the newly developed tourmaline reference material BR-DG68. Overall, current and future studies in geochemistry may benefit from these newly proposed tourmaline RMs, which should lead to significantly improved precision and accuracy for in situ B isotope and elemental measurement.

研究领域: 地质学 · 地球化学
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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

A green and facile direct ink writing technique for preparation calibration standards in laser ablation inductively coupled plasma mass spectrometry analysis

Wenxin Cui,Haohao Ji,Zhaoqing Cai,Qing Li,Dengguang Yu,Haiyan Luo,Jian Zhang,Zheng Wang

Background Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful tool for microanalysis of solid materials. Nevertheless, one limitation of the method is the lack of well-characterized homogeneous reference materials (RMs), such as BaF 2 crystal and BaCO 3 ceramics samples, making direct quantification difficult. This work presents a novel Direct Ink Writing (DIW) method to produce RMs for microanalysis. The Mg, Cr, Fe, Co, Ni, Cu, Y, Mo, Pr, Gd, Dy, Ho, Er, Tm, Yb, and Lu solutions were gravimetrically doped into BaCO 3 by mixing with the dispersant and then cured with DIW techniques. (94) Results BaCO 3 powder was combined with a dopant analyte to produce a printable slurry, aided by the use of a dispersant and cellulose . The resulting mixture was then printed using DIW equipment. The retention rates of the doped elements were investigated by internal and external standard method, and the results showed that they were completely dispersed in the solid material. After further optimization, it was found that there was no significant heterogeneity among the printed samples. LA-ICP-MS was used to analyze printed samples, to evaluate micro-scale homogeneity. The mass concentration of the doped element was determined by ICP-MS, verify its move closer to nominal value. Compared with the traditional reference materials preparation methods, the DIW technology greatly increased the sample homogeneity and the accuracy of the desired concentration. (132) Significance As far as we know, there are few reports on the application of DIW method to prepare calibration standards. In brief, it is proved that the proposed method of preparing calibration standard by DIW technique to quantify analytes is valid and robust. This procedure provides great potential for LA-ICP-MS in-situ analysis in the field of well-prepared products, such as ceramic and crystal samples. (63)

CAS / MDL: 7787-32-8
研究领域: 分析化学 · 材料科学
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY · 2020 ·Vol. 35 ·期 5 ·886-895 · IF 3.498

Development of REE-doped CaWO4 single crystals as reference materials for in situ microanalysis of scheelite via LA-ICP-MS

Yuqiu Ke,Jianzong Zhou,Xiaoqing Yi,Yijian Sun,Jianfeng Shao,Shiyong You,Wei Wang,Yunzhi Tang,Chaoyang Tu

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been widely used for in situ microanalysis of elemental concentrations in solid samples, but its application is hampered by a lack of matrix-matched and homogeneous reference materials (RMs). In this work, a new method for preparing matrix-matched and homogeneous LA-ICP-MS reference materials has been developed. A multiple rare earth element (REE) doped CaWO4 single crystal (CaW-1) was successfully prepared by the Czochralski technique. The matrix composition and crystal structure were confirmed by X-ray diffraction (XRD) and electron microprobe analysis (EMPA), which indicates that these crystals have a matrix composition of CaWO4 and are matrix-matched with natural scheelite. The homogeneity of REE distribution was systematically studied by seven methods and the results demonstrated that REEs are distributed homogeneously in the CaWO4 single crystal with slight fluctuation (RSDs: ca. 4%). It can be concluded that the synthesized CaWO4 single crystal meets both crucial requirements, matrix-matched and homogeneous distribution, for an LA-ICP-MS reference material, and therefore it was used to quantitatively calibrate REE concentrations in natural scheelite. The results showed that acceptable analytical errors (<8%) were obtained, which were more desirable than those obtained with non-matrix-matched NIST SRM 610 as the RM. It robustly validates the ability of the developed method for preparing CaWO4 single crystals as possible LA-ICP-MS reference materials to calibrate REE concentrations in natural scheelite.

研究领域: 矿物学 · 分析化学
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Open Digital Reference Materials Unchain Controlled Substance Analysis

Yu Tang,Sinan Wang,Cuifen Fang,Ruiqi Zheng,Ping Xu,J. Brent Friesen,Shao-Nong Chen,Yi Wang,Guido F. Pauli,Yiyu Cheng

Digital reference materials (dRMs) can conceptually overcome the intrinsically limited availability and accessibility of identical reference materials (iRMs) that persistently impede the chemical analysis of rare and controlled substances, respectively. Quantum mechanics (QM)-driven 1H iterative functionalized spin analysis (HifSA) is digital by nature and capable of referencing molecules with high specificity and full instrumental portability in the form of HifSA profiles by decoding their “nuclear genotype” in the form of the key 1H spin parameters including chemical shifts (δ) and coupling constants (J). This study establishes the proof-of-concept for replacing iRMs with open dRMs for controlled Ephedra alkaloids (ephedrine, pseudoephedrine, methylephedrine) by producing their fully field-scalable HifSA profiles and adopting them for the qualitative and quantitative analysis of E. sinica and traditional Chinese medicines as a E. sinica-containing multicomponent mixture. QM-derived qHNMR (QM-qHNMR) results were corroborated via classical integral-based qHNMR (INT-qHNMR) and HPLC-UV methods. Furthermore, extending this method to 12 congeneric phenylethylamines created a starting set of open dRMs within the space of controlled substances. The remarkable congruence and near-identical (within a few 10 mHz) coupling constants in the monosubstituted benzenes (AA′BB′C spin systems) cross-validated the trueness of the dRM profiles. In addition, QM-qHNMR analysis of Ephedra alkaloids across a range of magnetic field strength equivalent to 60–600 MHz for 1H confirm the portable nature of the dRMs and highlight their contribution to the sustainability and wider application in analytical chemistry. Practical aspects of HifSA profiling and QM-qHNMR are covered by comparing two software tools, Cosmic Truth (CT) and ChemAdder. Expanding the open dRM concept more broadly within chemical analysis advances the analytical toolbox for complex mixtures, fosters simultaneous identification and quantification of multiple target analytes, and eliminates the need for iRMs.

研究领域: 分析化学 · 光谱学 · 药物化学 · 量子化学 · 天然产物化学
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