Determination of Trace Silver in Geological Samples by Inductively Coupled Plasma-Mass Spectrometry with Acid Decomposition and Internal Standard Calibration
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摘要:
应用电感耦合等离子体质谱法（ICP-MS）测定地质样品中的痕量银时，Zr、Nb、Mo的氧化物以及氢氧化物对银的两个质量数107Ag和109Ag造成严重的质谱重叠干扰，导致结果有明显的偏差。针对此问题，本文基于107Ag的质谱干扰相对单一，只有90Zr16OH+和91Zr16O+对107Ag产生干扰，在ICP-MS分析中选用107Ag对银进行测定。样品前处理中采用氢氟酸、高氯酸、硝酸敞开消解，在浸提液中加入过量氨水，将107Ag的主要干扰元素Zr通过生成沉淀实现分离，以Re作内标补偿基体效应和信号漂移，采用ICP-MS测定了水系沉积物、岩石、土壤国家标准物质中痕量银的含量，测试值与认定值一致，方法检出限为0.0031μg/g，相对标准偏差（RSD）为4.38%。该方法简捷，在浸取液中加入氨水之前可以先测定常见金属元素，实现了浸取溶液的循环再利用。
Abstract:BACKGROUND Inductively coupled plasma-mass spectrometry (ICP-MS) is used for the determination of trace silver in geological samples. Hydroxides and oxides of Zr, Nb, Mo cause serious overlapping interference on the two mass numbers of 107Ag and 109Ag, which can result in a significant deviation of the results.
OBJECTIVES To develop a method for precise determination of trace Ag in geological samples.
METHODS Considering that the MS interference of 107Ag is relatively simple and only 90Zr16OH+ and 91Zr16O+ have interferences on 107Ag, 107Ag was selected for the determination of silver in ICP-MS analysis. In the sample pretreatment, hydrofluoric acid, perchloric acid and nitric acid were used for open digestion, and excessive ammonia was added to the extraction solution. The main interference element Zr of 107Ag was separated by precipitation. Trace silver was determined with Re as the internal standard to complement matrix effect and signal drift.
RESULTS The content of trace silver in national standard materials of stream sediment, rock and soil was determined by ICP-MS. The test value was consistent with the certified value. The detection limit of the method was 0.0031μg/g, and the relative standard deviation (RSD) was 4.38%.
CONCLUSIONS The method has the advantages of simple and accurate measurement of trace silver. Moreover, common metal elements can be determined before adding ammonia to the leaching solution, so that the extraction solution can be recycled.
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表 1 样品不同处理方式ICP-MS测定锆的强度对比
Table 1. Comparison of zirconium strength measured by ICP-MS with different sample pretreatment methods
样品处理条件 锆的强度(cps) 平行样1 平行样2 平行样3 王水溶解空白 2353.2 2387.4 2311.6 王水溶解GBW07309 83247.3 84118.3 84212.2 三酸溶解空白 2415.7 2378.4 2411.3 三酸溶解GBW07309 1018157.0 1054670.4 1034180.6 三酸溶解-氨水除锆处理GBW07309 2576.3 2502.7 2532.3 
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表 2 不同元素加标回收率对比
Table 2. Comparison of spiked recovery of different elements
分析元素 加标量
(μg/L)本法平行测定的银含量
(μg/ L)平均值
(μg/L)加标回收率
(%)Ag 5.00 4.88 4.90 4.87 4.90 4.89 97.82 4.89 4.86 4.91 4.92 Rh 5.00 2.33 2.38 2.33 2.34 2.38 46.55 2.31 2.33 2.30 2.30 Re 5.00 5.01 5.00 4.95 4.93 4.98 99.68 5.03 4.98 5.03 4.94
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表 3 方法精密度
Table 3. Precision tests of the method
GBW07309中Ag的认定值(μg/g) 本法测定的银含量(μg/g) RSD(%) 平行测定值 平均值 0.089±0.010 0.088 0.083 0.095 0.091 0.090 4.38 0.094 0.088 0.095 0.087 0.086 0.093 0.093 0.088
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表 4 方法准确度
Table 4. Accuracy tests of the method
标准物质编号 银含量(μg/g) 标准偏差允许范围
(μg/g)测定值 认定值 GBW07309 0.092 0.089 ±0.010 GBW07310 0.26 0.27 ±0.02 GBW07311 3.3 3.2 ±0.4 GBW07312 1.11 1.15 ±0.11 GBW07404 0.075 0.070 ±0.011 GBW07405 4.4 4.4 ±0.4 GBW07406 0.021 0.20 ±0.02 GBW07407 0.063 0.057 ±0.011
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