Determination of Germanium and Tellurium in Geological Samples by A Self-developed Hydride Generation Device Paired with Inductively Coupled Plasma-Mass Spectrometer
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摘要: 氢化物发生与ICP-MS联用(HG-ICP-MS)可降低基体效应和多原子离子干扰,本文自制了一种与ICP-MS联用的氢化物发生装置,该装置采用三通将酸、碱和试样引入多接头的混合反应器中,再经自行设计的气液分离器随载气进入等离子体中,据此建立了HG-ICP-MS测定地质样品中稀散元素锗和碲的分析方法。实验中以20%盐酸+2%硼氢化钾(0.1%氢氧化钾介质)作为最佳氢化物发生反应体系,0.95 L/min为最佳载气流量,获得分析信号的灵敏度和稳定性较高,连续测定20次Ge和Te信号强度的相对标准偏差分别为8.3%和2.1%,残余在ICP-MS中的Ge和Te信号强度在200 s内基本清洗完毕。Ge和Te检出限分别为0.007 μg/g和0.006 μg/g,其中Te检出限比采用敞口四酸溶样ICP-MS直接测定的检出限(0.1 μg/g)更低,应用于分析实际样品可给出准确结果。Abstract: Hydride generation paired with Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) can reduce the matrix effect and interference of polyatomic ions. In this study, one self-made hydride generation device coupled with ICP-MS was developed for the determination of scattered elements, Ge and Te, in geological samples. A Y-shaped connection pipe is used to introduce acid, alkali and the sample into a multiple-joint reactor. After the reaction is complete, the mixture of liquid and gas is separated by self-designed gas-liquid separator. Finally, the gaseous hydrides along with the carrier gas enter the plasma. In this experiment, 20% HCl and 2% KBH4 (0.1% KOH medium) were used as the hydride generation reaction system and the carrier gas flow rate was set to 0.95 L/min to keep high sensitivity and stability. The relative standard deviations of Ge and Te signal intensity for 20 times continuous determination are 8.3% and 2.1%, respectively. The residual Ge and Te in ICP-MS can be cleaned up within 200 s. The detection limits of this method are 0.007 μg/g and 0.006 μg/g for Ge and Te, respectively. Moreover, the detection limit of Te for this method is lower than that of Te (0.1 μg/g) determined by ICP-MS directly after four-acid digestion. Therefore, this method can be used to gain accurate results for Ge and Te contents in geological samples.
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表 1 岩石标准物质的测定结果和方法比对
Table 1. Analytical results of Ge and Te in rock reference materials and comparison of the different methods
标准物质编号 Ge Te 实际样品编号 Ge Te 推荐值(μg/g) 本方法测定值(μg/g) RSD(%)(n=5) 推荐值(μg/g) 本方法测定值(μg/g) RSD(%)(n=5) 本方法测定值(μg/g) 发射光谱测定值(μg/g) 本方法测定值(μg/g) ICP-MS直接测定值(μg/g) GBW07103 2 2.24 4.7 0.021 0.028 5.8 样品1 1.18 1.25 0.015 <0.1 GBW07105 0.93 1.04 5.8 0.017 0.015 4.1 样品2 1.10 1.02 0.018 <0.1 GBW07107 1.16 1.43 3.9 0.056 0.038 6.8 样品3 0.75 0.67 0.013 <0.1 GBW07108 3.1 3.10 3.8 0.038 0.056 3.3 样品4 1.72 1.70 0.025 <0.1 GBW07109 0.67 0.72 4.5 0.022 0.027 4.6 样品5 1.38 1.40 0.016 <0.1 
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