Study on the Determination of Silver, Boron, Molybdenum, Tin in Geochemical Samples by the Method of Solid Sampling Carrier Distillation Atomic Emission Spectrum
LI Zhi-xiong1, 2, LU Qian-shu1, ZHANG Lian-kai1, 2*, ZHANG Song1, YANG Wan-tao1, LI Can-feng1, FENG Jun1, LIU Zhen-chao1
1. Kunming Natural Resources Comprehensive Investigation Center, China Geological Survey, Kunming 650100, China
2. Key Laboratory of Karst Dynamics, Ministry of Natural Resources and Guangxi Zhuang Autonomous Region, Institute of Karst Geology, Chinese Academy of Geological Sciences, Guilin 541004, China
Abstract：Atomic emission spectrometry (AES) was widely used for the determination of silver (Ag), boron (B), molybdenum (Mo) and tin (Sn) in multi-target geochemical surveys, ecological geochemical assessment and International Geochemical Mapping Program (IGCP259/360). The carrier distillation technique based on Alternating Current (AC) arc powder method can effectively reduce the matrix effect and improve the fractionation process of the elements to be measured. By establishing the carrier distillation technique with aluminum oxide (Al2O3), barium carbonate (BaCO3), potassium pyrosulfate (K2S2O7), sodium fluoride (NaF), sulfur (S), ferric oxide (Fe2O3), teflon ([C2F4]n) as the main components, it was experimentally confirmed that the carrier buffer could well induce the reaction of oxidation, fluoridation and sulfurization. The evaporation process of elements such as Ag, B, germanium (Ge), Mo, and Sn was improved by adjusting a series of physical and chemical reactions to increase the volatilization of the elements to be measured and reduce the volatilization of the sample matrix elements. Scanning electron microscopy (SEM) showed that the carrier buffer formed a complex salt solid melt with the primary elements of the sample in the high-temperature arc, which can absorb CaO, SiO and other matrix oxides and suppress their interference with the components to measured, and the mutual synergy between the components of the carrier in the buffer promotes the reaction of each element in the cupro-graphite electrode. The evaporation curve showed that the carrier buffer could effectively control the evaporation process of each element, and the whole arc flame region is in thermodynamic equilibrium. The evaporation of each component to be measured was basically completed within 30 seconds, and the controlled excitation current can improve the signal-to-noise ratio and reduce the detection limits. On this basis, a new single electrode carrier distillation method for rapid determination of Ag, B, Ge, Mo, Sn and other elements in geochemical samples by AES-7200 direct reading emission spectrometer is established. The working curves of the elements to be measured had good linearity, the correlation coefficient was 0.997 21～0.999 37, and the detection limit of the method for Ag, B, Ge, Mo and Sn was 0.008, 0.646, 0.160 and 0.129 μg·g-1 respectively with the precision (RSD%) was in the range of 2.27~10.0, and the accuracy (Δ|logC|) was less than <0.1 respectively. Through a large number of analytical verification tests on aqueous sediments, soil and rock samples, the single electrode carrier distillation method can improve the sensitivity of the element to be measured and the accuracy of analysis results, and was suitable for the analysis of regional geochemical exploration samples of complex carbonate, silicate containing iron oxide and high bound water, which can satisfy the needs of different geochemical survey and eco-geochemical assessment in different regions.
李志雄，陆迁树，张连凯，张 松，杨万涛，李灿锋，冯 俊，刘振超. 固体进样发射光谱载体蒸馏法测定区域地球化学勘查样品中银硼钼锡的研究[J]. 光谱学与光谱分析, 2023, 43(07): 2132-2138.
LI Zhi-xiong, LU Qian-shu, ZHANG Lian-kai, ZHANG Song, YANG Wan-tao, LI Can-feng, FENG Jun, LIU Zhen-chao. Study on the Determination of Silver, Boron, Molybdenum, Tin in Geochemical Samples by the Method of Solid Sampling Carrier Distillation Atomic Emission Spectrum. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(07): 2132-2138.
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