<i>In situ</i> Quantitative Analysis of Chemical Composition of Lithium and Beryllium Minerals by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry

FAN Chenzi; SUN Dongyang; ZHAO Linghao; YUAN Jihai; HU Mingyue; ZHAO Ming

doi:10.15898/j.ykcs.202305310072

Rock and Mineral Analysis > 2024 > 43(1): 87-100. > DOI: 10.15898/j.ykcs.202305310072

FAN Chenzi，SUN Dongyang，ZHAO Linghao，et al. In situ Quantitative Analysis of Chemical Composition of Lithium and Beryllium Minerals by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry[J]. Rock and Mineral Analysis，2024，43（1）：87−100. DOI: 10.15898/j.ykcs.202305310072

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In situ Quantitative Analysis of Chemical Composition of Lithium and Beryllium Minerals by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry

1.
National Research Center for Geoanalysis, Beijing 100037, China
2.
State Key Laboratory of Mineral Processing, Beijing 102628, China

More Information

Received Date: May 30, 2023
Revised Date: August 29, 2023
Accepted Date: September 16, 2023
Available Online: November 07, 2023

Abstract

HIGHLIGHTS
(1) Helium gas flow rate has great influence on the accuracy of quantitative analysis of spodumene and beryl chemical composition by LA-ICP-MS.

(2) The increase of beam spot diameter is helpful for the precision of quantitative analysis of spodumene and beryl chemical composition by LA-ICP-MS.

(3) The matrix and content matching calibration materials are more conducive to quantitative calibration of lithium and beryllium by LA-ICP-MS.

ABSTRACT

Lithium and beryllium are the strategic key metals and the minerals such as spodumene and beryl are the main raw materials for extracting lithium and beryllium elements. In order to accurately analyze the minerals by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), the quantitative analytical procedure needs to be improved to reduce the matrix effect caused by non-matrix matching calibration. In the research, a New Wave 193nm ArF excimer laser and an Element Ⅱ high resolution inductively coupled plasma-mass spectrometer were used and the working parameters of the instrument optimized. The analytical results show that Li and Be light elements can quantitatively be determined by the suggested method. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202305310072.
- LA-ICP-MS,
- lithium mineral,
- beryllium mineral,
- gas flow,
- laser spot size
BRIEF REPORT
Significance: Lithium and beryllium are strategic key metals worldwide. Minerals such as spodumene and beryl are the main raw materials containing lithium and beryllium elements. The electron probe method commonly used in micro-areas cannot accurately quantify light elements with low energy. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) needs to be improved to reduce the matrix effect caused by non-matrix matching calibration and improve the accuracy and precision of analysis. We developed an in situ quantitative analysis method of lithium and beryllium elements in natural mineral samples by LA-ICP-MS in order to give analytical technical support for the efficient utilization of lithium and beryllium resources. Our results indicate that LA-ICP-MS can be used to determine Li and Be light elements quantitatively in minerals by optimizing the working parameters of the instrument, especially the flow rate of He and the quantitative calibration method. It provides strong technical support for the study of the occurrence state and metallogenic enrichment mechanism of strategic lithium and beryllium resources.

Methods: A New Wave 193nm ArF excimer laser and an Element Ⅱ inductively coupled plasma high resolution mass spectrometer were used. The laser ablation system used in the comparison experiment was UP213 Nd:YAG garnet solid laser. The samples used here included beryl C12 and spodumene K32 calibration samples, the content values of which were provided by the Electron Probe Microbeam Analysis Laboratory of Mineral Resources Institute, Chinese Academy of Geological Sciences. In addition, the minerals beryl B1 and spodumene L1 with high purity and large crystal size were collected for experimental analysis. The chemical constituents Si, Al and Be of beryl B1 were determined by X-ray fluorescence spectrometry (XRF), electron probe microanalysis (EPMA) and alkali fusion inductively coupled plasma-optical mass spectrometry (ICP-OES), respectively. The chemical composition of Li, Si and Al in spodumene L1 were determined by XRF and atmospheric pressure liquid cathode glow discharge spectrometer. The external reference materials used for LA-ICP-MS were NIST610, GSE-1G and CGSG-4.

Data and Results: The effects of LA-ICP-MS instrument working conditions (isotope selection and counting mode, He flow rate, Ar flow rate, beam spot diameter, energy density) and data processing methods (external reference material, internal standard element) on the precision and accuracy of Li and Be quantitative analysis results were discussed. The experimental results show that the flow rate of He and Ar gas not only affects the signal intensity of Li and Be, but also the relative error can be reduced by appropriately reducing the flow rate of He (0.6L/min). The ionization energy of Li (first ionization energy of Li 520.2kJ/mol) is lower than that of Si (786.5kJ/mol). The effect of mass loading would make the relative sensitivity factor of Li/Si in the standard material and samples vary, with the airflow inconsistent due to different contents. Although increasing the beam spot diameter can increase the data precision by more than 10%, it has little effect on the accuracy. However, the size of the beam spot diameter often affects the uniformity of aerosol particles and the amount of sample introduced into the ICP, which may reduce the effects of elemental fractionation and instrument drift. For transparent minerals with high hardness such as beryl, the energy density (relative strength >75%, fluence >2.7J/cm²) should be increased to ensure effective ablation. GSE-1G, which has a higher content in existing standards, was selected for calibration of ⁷Li, and NIST610 was selected for calibration of ⁹Be, and Al was used as the internal standard compensation element. However, the content of Al is less than Si in these standard samples. So, it is necessary to use Al as the internal standard element when the instrument is running stably.

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In situ Quantitative Analysis of Chemical Composition of Lithium and Beryllium Minerals by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry