Determination of Uraniumand Thorium in Sandstone Uranium Deposits by Inductively Coupled Plasma-Optical Emission Spectrometry with Microwave Digestion
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摘要:
砂岩型铀矿是重要的战略性矿产资源，分析铀钍元素含量对砂岩型铀矿的矿床评价和综合利用有重要意义。砂岩型铀矿中铀钍元素的分析目前主要采用酸溶和碱熔方式处理样品，电感耦合等离子体发射光谱法(ICP-OES)进行检测。敞口酸溶法处理样品时往往分解不完全导致结果偏低，碱熔法过程冗长，不利于快速检测，且砂岩型铀矿中铁元素含量很高会对铀钍测量产生干扰。采用微波消解对样品进行处理，在盐酸提取液中加入EDTA和三乙醇胺混合溶液作为掩蔽剂，与溶液中的铁离子形成配合物有效地消除了共存元素铁对铀钍测定的干扰。实验优化了各元素的分析谱线，对掩蔽剂用量进行对比试验以获得最佳条件，采用干扰校正系数法基本消除了共存元素的谱线干扰。标准曲线线性相关系数大于0.9995，方法检出限铀为0.70μg/g，钍为0.58μg/g，标准物质测定结果的相对误差为1.47%~1.82%，相对标准偏差(RSD，n=12)为1.32%~1.78%。该方法操作简单，能够准确地同时测定砂岩型铀矿中的铀和钍元素。
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关键词:
- 砂岩型铀矿 /
- 微波消解 /
- EDTA /
- 三乙醇胺 /
- 电感耦合等离子体发射光谱法
Abstract:BACKGROUND Sandstone-type uranium deposits are important strategic mineral resource. Rapid and accurate analysis of uranium and thorium content is of great significance to the evaluation and comprehensive utilization of this type of deposit. At present, the analysis of uranium and thorium is mainly determined by acid dissolution and alkali fusion methods to decompose samples. For the open acid dissolution method, the decomposition is often incomplete, resulting in lower results. The alkali fusion process is lengthy, which is not conducive to rapid detection. In addition, the high content of iron elements in sandstone type uranium deposits interfere with the measurement of uranium and thorium.
OBJECTIVES To develop a method which can determine uranium and thorium in sandstone uranium deposits by inductively coupled plasma-optical emission spectrometry (ICP-OES) with microwave digestion.
METHODS The samples were treated by microwave digestion technology, EDTA and triethanolamine mixed solution were added to the hydrochloric acid extract as masking agents to form a complex with iron ions in the solution, which effectively eliminated the interference of coexisting elemental iron on the determination of uranium and thorium. The experiment optimized the analytical spectral lines of each element, compared the amount of masking agent to obtain the best conditions, and basically eliminated the spectral line interference of coexisting elements by using the interference correction coefficient method.
RESULTS The linear correlation coefficients of standard curves were greater than 0.9995, and the detection limit of uranium and thorium were 0.70μg/g, and 0.58μg/g, respectively. The relative error of the determination results of reference materials was 1.47%-1.82% and the relative standard deviation (RSD, n=12) was 1.32%-1.78%.
CONCLUSIONS The method is simple to operate, effectively masking the interference of iron on uranium and thorium, and can be used to accurately complete the simultaneous determination of uranium and thorium in sandstone-type uranium deposits.
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表 1 微波消解升温程序
Table 1. Program of microwave digestion
步骤 升温时间(min) 功率(W) 温度(℃) 保持时间(min) 1 5 1200 100 0 2 5 1200 130 5 3 5 1200 180 20 
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表 2 国家标准物质GBW04106采用不同样品分解方式测定结果
Table 2. Analytical results of elements in GBW04106 dissoluted with different digestion methods
溶样方式 用酸量(mL) 溶样时间(h) 溶样温度(℃) 铀测定值(%) 钍测定值(%) 敞口酸溶高压密闭消解 252.5 427 160190 0.04760.0502 0.1370.157 微波消解 8 1.5 180 0.0495 0.151
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表 3 国家标准物质GBW04106在不同谱线下的测定结果
Table 3. Analytical results of elements in GBW04106 by different spectral lines
标准值(%) 不同谱线下GBW04106中铀的测定值(%) 标准值(%) 不同谱线下GBW04106中钍的测定值(%) 367.007nm 385.958nm 393.203nm 409.014nm 283.730nm 339.204nm 401.913n 0.0504 0.0257 0.0611 0.124 0.0498 0.156 0.097 0.182 0.153
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表 4 有铁干扰时加入不同掩蔽剂铀的测定结果
Table 4. Analytical results of uranium with different masking agents in the presence of iron interference
分析谱线(nm) 5μg/mL铀标准溶液中铀测量值(μg/g) 10μg/mL铀标准溶液中铀测量值(μg/g) 步骤1 步骤2 步骤3 步骤1 步骤2 步骤3 铀标准溶液(5μg/mL) 加Fe3+量(100mg/L) 加掩蔽剂(10mL) 铀标准溶液(10μg/mL) 加Fe3+量(200mg/L) 加掩蔽剂(10mL) 367.007 4.897 6.102 5.237 9.883 11.21 10.25 385.958 5.023 5.933 5.253 10.13 10.88 10.27 393.203 5.012 5.935 5.398 10.25 10.91 10.31 409.014 5.003 5.698 4.987 10.05 10.73 10.03
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表 5 方法准确度和精密度
Table 5. Accuracy and precision tests of the method
技术指标 GBW04101铀含量 GBW04106钍含量 标准值(%) 3.29 0.156 测定平均值(%) 3.34 0.159 相对误差(%) 1.52 1.92 RSD(%) 1.32 1.78
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