Determination of 14 Trace Elements in Geochemical Samples by ICP-MS Using Kinetic Energy Discrimination Mode
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摘要: 应用传统ICP-MS法测定勘查地球化学样品中Ag、Cd等痕量元素，基体效应和多原子离子干扰严重，准确测定的难度较大。本文基于当前ICP-MS消除干扰技术，分析了ICP-MS标准模式（STD）及动能歧视模式（KED）测定地球化学样品中Ag、Cd等14种痕量元素的有效性，通过比较这两种模式的测定效果，在此基础上确定了各元素的有效测定模式。结果表明：在KED模式下，基体元素如Zr、Nb氧化物的产率降低，基本上消除了Zr、Nb氧化物对痕量元素Ag、Cd的多原子离子干扰。KED模式提高了信噪比，降低了方法检出限，如Ag、Cd的检出限分别为0.004mg/kg、0.005mg/kg，其他12种元素的检出限也低于多目标地球化学调查76种元素分析方案中的检出限。测定痕量元素的准确度显著优于STD模式。实验中采用简单的硝酸-氢氟酸-高氯酸消解样品，残渣用王水复溶，结合KED模式下优选出干扰较小的同位素作为测定同位素，以Rh作为内标校正仪器产生的信号漂移，将样品溶液稀释至1000倍，基体效应降低至最小。本方法经国家一级标准物质的验证，测定结果与认定值相符，可为勘查地球化学提供高质量数据。Abstract:
BACKGROUNDTraditional inductively coupled plasma-mass spectrometry (ICP-MS) determination of trace elements such as Ag and Cd in geochemical samples is seriously affected by the matrix effect and multiple polyatomic ions, making it difficult to measure these elements accurately. OBJECTIVESTo compare the results of ICP-MS standard mode (STD) and kinetic energy discrimination mode (KED), and determine the valid determination modes of each element. METHODSThe samples were digested by HNO3-HF-HClO4, and the residue was dissolved in aqua regia. Under the KED mode, the isotopes with less interference were selected as the determination isotopes. Rh was used as the internal standard element to correct the signal drift, and the sample solution was diluted by 1000. Under these conditions, the matrix effect was minimized. RESULTSThe productivity of matrix elements such as Zr and Nb oxides was reduced, and the interference of oxides on Ag and Cd was minimized under the KED mode. The KED mode improved the signal-to-noise ratio and reduced the detection limits of this method with Ag and Cd, detection limits of 0.004mg/kg and 0.005mg/kg, respectively. The detection limits of the other 12 elements were also lower than those of 76 element analysis schemes in a multi-objective geochemical survey. The accuracy of determination of trace elements was significantly better than that of the STD mode. CONCLUSIONSThe method has been verified by the first-class national reference material and the analytical results are in good agreement with the certified values. The method provides high-quality data for exploration geochemistry. -
Key words:
- rock /
- soil /
- sediment /
- Ag /
- Cd /
- acid dissolution /
- inductively coupled plasma-mass spectrometry /
- kinetic energy discrimination
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表 1 干扰元素的实验结果
Table 1. Results of interference elements
干扰元素 标准溶液浓度
(mg/L)测定元素 质量数 干扰系数 Sn 50 Cd 114 0.023 50 In 115 0.012 Zr 50 Mo 96 0.081 50 Ag 107 0.001 50 Ag 109 0.0001 50 Cd 111 0.0001 Nb 50 Ag 109 0.0020 Cd 1 In 113 1.083 
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表 2 STD和KED模式测定结果的对比
Table 2. Comparison of the analytical results of Ag and Cd in STD and KED modes
标准物质编号 Ag Cd 认定值
(mg/kg)STD
测定值
(mg/kg)相对误差
(%)KED
测定值
(mg/kg)相对误差
(%)认定值
(mg/kg)STD
测定值
(mg/kg)相对误差
(%)KED
测定值
(mg/kg)相对误差
(%)GBW07103 0.033 0.15 355 0.034 3.0 0.029 0.07 141 0.037 27.6 GBW07408 0.06 0.19 217 0.07 16.7 0.13 0.18 38 0.15 15.4 GBW07358 0.14 0.23 64 0.14 0 0.34 0.33 -3.0 039 14.7
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表 3 方法检出限
Table 3. Detection limit of the method
元素 方法检出限
(mg/kg)Co 0.006 Ni 0.12 Cu 0.14 Zn 0.6 Mo 0.023 Ag 0.004 Cd 0.005 In 0.002 Sb 0.017 Cs 0.006 Ta 0.005 W 0.02 Pb 0.27 Bi 0.024
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表 4 方法精密度和准确度
Table 4. Precision and accuracy tests of the method
元素 GBW07103(岩石) GBW07104(岩石) GBW07402(土壤) GBW07408(土壤) GBW07358(水系沉积物) GBW07366(水系沉积物) 认定值
(mg/kg)测定平均值
(mg/kg)RSD
(%)相对误差
(%)认定值
(mg/kg)测定平均值
(mg/kg)RSD
(%)相对误差
(%)认定值
(mg/kg)测定平均值
(mg/kg)RSD
(%)相对误差
(%)认定值
(mg/kg)测定平均值
(mg/kg)RSD
(%)相对误差
(%)认定值
(mg/kg)测定平均值
(mg/kg)RSD
(%)相对误差
(%)认定值
(mg/kg)测定平均值
(mg/kg)RSD
(%)相对误差
(%)Co 3.4 3 3.4 -13.0 13.2 13.2 3.3 -0.1 8.7 8.0 3.8 -7.5 12.7 12.4 2.7 -2.3 10.2 9.5 5.2 -6.5 14.4 14.2 4.5 -1.7 Ni 2.3 1.9 10.3 -16 17 16.8 3.7 -1.4 19.4 18.8 3.7 -3.2 31.5 31.1 2.4 -1.4 18.6 18.1 11 -2.9 29 29 8 -1.0 Cu 3.2 2.6 3.8 -20 55 56.3 5.5 2.4 16.3 15.3 3.6 -6.3 24.3 23.4 2.0 -3.8 132 126 5.3 -4.4 483 487 4.1 0.7 Zn 28 28 5.2 -0.03 71 72.6 2.9 2.3 42 41 3.6 -1.7 68 68 1.9 -0.6 208 205 5.5 -1.3 874 875 4.2 0.1 Mo 3.5 3.6 5.1 2.5 0.54 0.62 6.5 14.0 0.98 0.98 4.9 -0.01 1.16 1.18 2.4 2.1 0.93 0.86 7.2 -7.0 1.56 1.49 6.2 -4.4 Ag 0.033 0.028 15.0 -15.0 0.071 0.076 6.9 7.0 0.054 0.054 7.6 0.9 0.06 0.063 7.2 5.3 0.14 0.14 6.2 -2.6 2.1 2.05 5.8 -2.2 Cd 0.029 0.033 18.0 14.0 0.061 0.072 7.8 18.0 0.071 0.077 5.3 7.9 0.13 0.14 7.7 6.9 0.34 0.32 7.3 -5.4 4.8 4.53 4.2 -5.7 In 0.02 0.019 13.0 -5.0 0.037 0.031 9.0 -16.0 0.09 0.092 5.9 2.1 0.044 0.052 7.8 18.0 0.14 0.14 6.1 0.9 0.37 0.37 6.0 0 Sb 0.21 0.23 9.5 8.3 0.12 0.1 14.6 0.3 1.3 1.3 5.9 2.3 1 1.2 4.3 20.0 1.18 1.17 6.4 -0.8 25 23.0 4.1 -9.0 Cs 38.4 40.1 3.7 4.4 2.3 1.9 3.2 -16.0 4.9 4.7 4.0 -3.6 7.5 7.7 2.3 3.3 5.8 5.6 4.9 -3.6 10.3 10.3 4.1 0 Ta 7.2 9.2 4.5 28.0 0.4 0.48 11.8 21.0 0.78 0.68 11.0 -13.0 1.05 1.14 8.7 8.2 0.65 0.58 17.0 -10.0 1.23 1.17 9.2 -4.8 W 8.4 9.3 3.7 11.0 0.45 0.53 8.6 17.0 1.08 1.15 11.0 6.3 1.7 1.8 2.9 7.9 2 1.9 5.6 -4.8 15.5 13.7 6.3 -11.9 Pb 31 33 3.6 5.1 11.3 10.2 3.5 -10.0 20 19 3.7 -3.3 21 19 2.3 -9.0 210 203 5.0 -3.3 127 128 4.0 0.4 Bi 0.53 0.54 5.9 1.4 0.081 0.1 10.2 -15.0 0.38 0.37 3.5 -3.8 0.3 0.3 2.7 -0.3 0.51 0.49 5.9 -3.8 13.1 13.0 4.3 -0.6
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