Determination of Cd in Environmental Geological Samples by Inductively Coupled Plasma-Mass Spectrometry with Membrane Desolvation
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摘要: 应用电感耦合等离子体质谱法（ICP-MS）分析环境地质样品中的Cd时，Zr、Mo元素的氧化物和氢氧化物会对Cd造成严重干扰，导致结果有明显的偏差。针对此问题，本文建立了膜去溶-ICP-MS直接测定环境地质样品中微量Cd的分析方法，该方法可有效地消除Zr、Mo氧化物和氢氧化物对Cd的干扰，保证结果准确、可靠。膜去溶-ICP-MS相比于常规ICP-MS测定Cd的方法，可将Zr、Mo氧化物和氢氧化物对Cd的干扰降低到0.001%，检测灵敏度提高3.5倍左右。在给定条件下，Cd的检出限为0.28 ng/L，测定下限为2.2 ng/L，精密度（RSD，n=12）为2.2%。利用该方法分析20种岩石、土壤和沉积物国家标准物质的测定值与标准值相符，表明膜去溶-ICP-MS法直接测定环境地质样品中痕量或超痕量Cd时具有一定的应用潜力。同时，用该方法对2016年中核集团组织的实验室间两个比对样品中的Cd进行测定，稳健Z比分数分别为0.500和-0.964，Z的绝对值都小于2。
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关键词:
- 膜去溶 /
- 电感耦合等离子体质谱法 /
- 镉 /
- 环境地质样品
Abstract: Cadmium suffers from significant Zr and Mo based oxide/hydroxide interferences during Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) analysis of environmental samples, which can result in a significant deviation of the results. Direct determination method of Cd in environmental geological samples by ICP-MS with membrane desolvation has been developed in this study. This method can effectively eliminate the interference of Zr, Mo oxides and hydroxides, and ensure the results are accurate and reliable. Compared with the conventional method of ICP-MS, the interference of Zr and Mo oxides and hydroxides can be reduced to 0.001% when membrane desolvation is used. Meanwhile, the sensitivity of Cd can be increased 3.5 times. Under the given conditions, the detection limit of Cd was 0.28 ng/L, the lower limit of determination was 2.2 ng/L, and the precision (RSD, n=12) was 2.2%. The method was applied to analyze 20 Chinese environmental geological reference materials. The analytical results are consistent with the certificated values. It indicates that the proposed method has a great potential for the direct determination of trace or ultra-trace levels of cadmium in environmental geological samples. At the same time, the method was used to determine Cd in two comparison samples between two laboratories in 2016. This comparison was organized by the China National Nuclear Corporation. The Z-scores were 0.500 and -0.964, respectively for the two laboratories, and the absolute values of Z were less than 2.
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致谢: 感谢国家地质实验测试中心温宏利教授级高级工程师在样品处理和测试工作中的帮助和指导。
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图 1 在膜去溶-ICP-MS测量条件下，吹扫气流速对(a) 94Zr 16OH+/90Zr和(b) 111Cd信号的影响
Figure 1. Variation of the signal intensities of (a) 94 Zr16OH+/90Zr and (b) 111Cd with sweep gas flow rate
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图 2 在膜去溶-ICP-MS测量条件下，N2的流速对(a) 94 Zr16OH+/90Zr和(b) 111Cd信号的影响
Figure 2. Variation of the signal intensities of (a) 94 Zr16OH+/90Zr and (b) 111Cd with N2 flow rate
表 1 仪器工作参数
Table 1 Operating conditions of the instruments
ICP-MS工作参数 膜去溶系统工作参数 仪器型号 iCAP Q 仪器型号 Aridus Ⅱ RF射频功率 1250 W 吹扫气流速 2.0~8.0 L/min 雾化气流速 0.89 mL/min 氮气流速 0~20 mL/min 辅助气流速 0.80 mL/min 喷射腔温度 110℃ 冷却气流速 13.0 mL/min 膜去溶温度 160℃ 跳峰 3点/质量 雾化气流速 0.7~1.0 L/min 信号采集方式 脉冲 
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表 2 方法精密度
Table 2 Precision tests of the method
Cd的标准值
(μg/g)Cd的本法测定值
(μg/g)平均值
(μg/g)RSD
(%)0.060±0.022 0.050 0.052 0.049 0.050
0.049 0.049 0.050 0.049
0.050 0.052 0.049 0.0500.050 2.2
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表 3 标准物质分析结果
Table 3 Analytical results of reference materials
标准物质
编号Cd含量(μg/g) 测定值 标准值 GBW07103 0.016 0.029±0.014 GBW07104 0.051 0.061±0.014 GBW07105 0.066 0.067±0.016 GBW07106 0.044 0.060±0.016 GBW07107 0.011 0.033±0.017 GBW07108 0.061 0.070±0.020 GBW07113 0.138 0.140±0.030 GBW07304 0.180 0.190±0.020 GBW07305 0.800 0.820±0.050 GBW07307 1.010 1.050±0.060 GBW07309 0.230 0.240±0.040 GBW07310 1.030 1.120±0.080 GBW07311 2.030 2.300±0.200 GBW07312 3.700 4.000±0.300 GBW07401 4.000 4.300±0.600 GBW07403 0.050 0.060±0.022 GBW07404 0.320 0.350±0.060 GBW07405 0.390 0.450±0.060 GBW07406 0.140 0.130±0.030 GBW07408 0.120 0.130±0.020
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表 4 使用膜去溶和未使用膜去溶对111Cd测定结果对比
Table 4 A comparison of measurement results for 111Cd with and without membrane desolvation, respectively
标准物质和
实际样品Cd的测定值(μg/g) 未使用膜去溶 使用膜去溶 GBW07113 0.572
0.5810.136
0.137Albriug-09 0.361
0.3650.068
0.065Albriug-10 1.02
1.040.351
0.352
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