Determination of 32 Trace Elements in Granite Pegmatite by Inductively Coupled Plasma-Optical Emission Spectrometry and Mass Spectrometry with Closed Acid Dissolution

XIA Chuanbo; CHENG Xuehai; JIANG Yun; ZHANG Wenjuan; CHEN Minggui; ZHAO Wei

doi:10.15898/j.ykcs.202307310105

Rock and Mineral Analysis > 2024 > 43(2): 247-258. > DOI: 10.15898/j.ykcs.202307310105

XIA Chuanbo，CHENG Xuehai，JIANG Yun，et al. Determination of 32 Trace Elements in Granite Pegmatite by Inductively Coupled Plasma-Optical Emission Spectrometry and Mass Spectrometry with Closed Acid Dissolution[J]. Rock and Mineral Analysis，2024，43（2）：247−258. DOI: 10.15898/j.ykcs.202307310105

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Determination of 32 Trace Elements in Granite Pegmatite by Inductively Coupled Plasma-Optical Emission Spectrometry and Mass Spectrometry with Closed Acid Dissolution

XIA Chuanbo^{1, 2,},
CHENG Xuehai^{1, 2},
JIANG Yun^{1, 2},
ZHANG Wenjuan^{1, 2},
CHEN Minggui^{1, 2},
ZHAO Wei^{1, 2, ,}

1.
Shandong Institute of Geological Sciences, Jinan 250013, China
2.
Shandong Provincial Key Laboratory of Metallogenic Geological Process and Resource Utilization, Jinan 250013, China

More Information

Received Date: July 30, 2023
Revised Date: January 29, 2024
Accepted Date: February 06, 2024
Available Online: April 28, 2024

Abstract

HIGHLIGHTS
(1) The granite pegmatite sample was digested by the closed dissolution method with HF and HNO₃, achieving complete decomposition of insoluble minerals.

(2) Aqua regia was used instead of HNO₃ for residual redissolution, promoting the redissolution of elements such as Nb, Ta, Zr, Hf and rare earth elements.

(3) Hydrofluoric acid and tartaric acid were avoided in the sample solution, making it more suitable for instrument analysis such as ICP-OES/MS.

ABSTRACT

Accurate determination of large ion lithophile elements, high field strength elements and rare earth elements in granite pegmatite can be used to judge the source of ore-forming fluid materials and the diagenetic tectonic environment. There are some problems in the sample determination process, such as incomplete decomposition of insoluble minerals and low recovery of elements like Zr, Hf, Th, U and rare earth elements. This article compared the decomposition effects of three methods. The results indicate that the two open digestion methods can lead to lower test results for elements such as Zr, Hf, and W, etc. In the closed digestion method, aqua regia was used instead of HNO₃ for residual redissolution, which promotes the redissolution of elements such as Nb, Ta, Zr, Hf, rare earth elements, etc. ICP-OES and ICP-MS can accurately determine 32 trace elements in granite pegmatite. The detection limit of the method was between 0.004μg/g and 2.50μg/g, with a precision of 1.0%−8.3% (RSD, n=12). The method was applied to the determination of 8 types of granite, pegmatite, rare metal ore reference materials and 3 types of actual samples. The measured values of the reference materials were consistent with the standard values. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202307310105.
- granite pegmatite,
- rare metal elements,
- rare earth elements,
- closed acid dissolution,
- ICP-OES/MS
BRIEF REPORT
Significance: Granite pegmatite is rich in Li, Be, Rb, Cs, Nb, Ta and other rare metal elements. Accurate determination of large ion lithophile elements (LILEs), high field strength elements (HFSEs) and rare earth elements (REEs) can be used to judge the source of ore-forming fluid materials, diagenetic tectonic environment and other studies^[1,11-13]. This article uses the closed digestion method to decompose granite pegmatite samples. The use of aqua regia instead of nitric acid for residual redissolution promotes the redissolution of elements such as Nb, Ta, Zr, Hf and REEs through the complexation effect of chloride ions. This solves the problems of incomplete decomposition of insoluble minerals and low recovery rates of elements such as Zr, Hf, Th, U and REEs. A method was established for the determination of 32 rare metal elements, REEs, and other elements in granite pegmatites using inductively coupled plasma-optical emission spectrometry and mass spectrometry (ICP-OES/MS). The method was applied to the determination of three actual samples and rare metal reference materials, and achieved good results.

Methods: The decomposition effects of three methods were compared. These methods were open digestion with HCl, HNO₃, HF and HClO₄^[7], open digestion with HCl, HNO₃, HF, HClO₄ and H₂SO₄^[9], and closed digestion with HNO₃ and HF, respectively. ICP-OES/MS were used for the determination of 32 elements.

Data and Results: (1) Comparison of three sample decomposition methods (Fig.1). ① For the four acid digestion method, the measured values of Li, Be, Rb, Cs and Ga were consistent with the standard values, but the values of Nb, Ta, Zr, Hf, W and REEs, especially heavy REEs, were severely low. ② For the five acid digestion method, the measured values of Li, Be, Rb, Cs and Ga were consistent with the standard values. The test results of easily hydrolysable elements such as Nb, Ta, and W were also consistent with the standard values. The extremely high content of Ta also provided a good recovery rate. However, the measurement results of Zr and Hf were generally low; the results of light rare earth elements such as La, Ce, Pr, and Nd in some standard materials were relatively low; the precision of the determination of Ba and Pb elements was very poor, sometimes severely low; the measured values of Tl were generally high. ③ For the closed acid dissolution method, 32 elements including Li, Be, Rb, Cs, Ga, Nb, Ta, Zr, Hf, W and REEs achieved good decomposition and recovery, and the measured values were consistent with the standard values. For the standard substance GBW07185 with extremely high Nb and Ta content, a small amount of white precipitate was generated, resulting in lower results for elements such as Nb, Ta and W.

　　(2) Technical indicators of analysis method. The detection limit for 32 elements was 0.004−2.5μg/g (Table 1). The relative standard deviation (RSD) of the measured values was 1.0%−8.3%. The average value of reference materials determination was consistent with the standard value, and the relative error (RE) of most elements was less than 10% (Table 2).

　　(3) Determination of actual samples. This method was applied to the determination of three types of actual samples and compared with the test results of the five acid method^[9] and the sodium peroxide alkali melting-hydrochloric acid acidification method^[26]. The results (Table 3) indicate that for Nb, Ta, W and Sn elements, the measured values by the closed method were consistent with those obtained by the alkali melting method.

　　Based on the test data, chondrite-normalized REE patterns and a primitive mantle-normalized trace element spider diagram were drawn. As shown in Fig.2, the results conform to the general characteristics of REEs distribution in granite pegmatites, and the trace element spider diagram is consistent with the geological laws reported in the literature^[11-13].

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References (30)

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