Inductively Coupled Plasma-Mass Spectrometric Analysis of Mercury in Biological Samples and Interference Correction Methods
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摘要:
电感耦合等离子体质谱法(ICP-MS)在测定生物样品中的Hg时，由于Hg元素的电离能高、电离效率低，且存在W的氧化物等多原子离子干扰，很难进行直接准确测定，加之生物样品中有机质含量高，基体复杂，也会导致分析结果产生偏差。本文通过比较标准模式(STD)和动能歧视模式(KED)下测定Hg的质谱干扰情况，表明在STD模式下200Hg、202Hg均受到W、Re、Os、Er、Dy等元素多原子离子的干扰，而KED模式有效地降低了干扰；在KED模式下选择202Hg作为分析同位素，Er、Dy、Re、Os等对Hg的干扰可以忽略不计，而W的氧化物干扰仍难以完全消除。进而详细研究了KED模式下W对Hg测定的质谱干扰，Hg所受干扰程度与W含量呈线性相关(R2=0.9997)，可利用KED模式结合数学校正法消除W的质谱干扰；优选了样品稀释倍数和内标元素，选择稀释倍数为100倍，50μg/L的Rh作为内标补偿基体效应。在此基础上建立生物样品中Hg的ICP-MS分析与干扰校正方法，检出限为1.2ng/g。采用该方法对9个标准物质中Hg含量进行测定，测定值与标准值(或参考值)一致，尤其是国家标准物质GBW10028(黄芪)、GBW10025(螺旋藻)、GBW10015a(菠菜)的准确度显著提高，相对标准偏差(n=10)为0.7％～7.0％。该方法操作简便，适用于W含量范围在0～1000ng/g，Hg含量范围在3.2～670ng/g的生物样品的测试。
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关键词:
- 生物样品 /
- 汞 /
- 电感耦合等离子体质谱法 /
- 干扰校正
Abstract:It is difficult to directly and accurately determine Hg in biological samples using inductively coupled plasma-mass spectrometry (ICP-MS) due to polyatomic interferences, such as tungsten oxide, and matrix effects. We established an ICP-MS method for the determination of Hg in biological samples based on the kinetic energy discrimination (KED) mode combined with mathematical correction and internal standard correction. In this experiment, spectral interferences of Hg in standard (STD) mode and KED mode were investigated. 202Hg was selected as the analyzed isotope in the KED mode, effectively reducing but not completely eliminating the interference. It was found that the interference amount of W with Hg was linearly related to the concentration of W (R2=0.9997). The matrix interference was eliminated with internal standard (Rh concentration of 50μg/L) and sample dilution (dilution of 100 times). The reliability of the method was tested with 9 reference materials, and the results were in agreement with certified values (or reference values). In particular, the accuracy of GBW10028 (Astragalus membranaceus), GBW10025 (spirulina) and GBW10015a (spinach) was significantly improved. The relative standard deviation (n=10) was 0.7% to 7.0%. The method is suitable for the analysis of Hg in biological samples.
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表 1 汞同位素丰度和潜在的多原子离子干扰
Table 1. Hg isotope abundance and potential polyatomic interferences
汞同位素 丰度(%) 潜在的多原子离子干扰 200Hg 23.10 16O+184W，14N+186W，40Ar+160Gd，16O+1H+183W，
12C+188Os，40Ar+160Dy，14N+186Os，13C+187Re，16O+3H+181Ta202Hg 29.86 16O+1H+185Re，16O+186W，12C+190Os，40Ar+162Dy，14N+188Os， 16O+186Os，15N+187 Re，13C+189Os，
40Ar+162Er，36Ar+166Er
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表 2 不同内标测定数据对比
Table 2. Comparison of analytical results with different internal standards
标准物质编号 名称 Hg标准值
(ng/g)W测定值
(ng/g)Hg测定值(ng/g) Hg测定值与标准值的相对误差(%) 无内标 Rh校正 Bi校正 无内标 Rh校正 Bi校正 GBW10052 绿茶 8.1±1.5 33.8 6.4 8.2 8.2 −21.0 1.2 1.2 GBW10048 芹菜 14.6±2.4 20.5 8.6 15.4 17.0 −41.1 5.5 16.4 GBW10015 菠菜 20±3 23.9 14.2 22.9 24.1 −29.0 14.5 20.5 GBW10023 紫菜 16±4 37.6 9.9 17.2 17.6 −38.1 7.5 10.0 GBW10020 柑橘叶 150±20 60.8 97.8 140 141 −34.8 −6.9 −5.9
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表 3 方法准确度和精密度
Table 3. Analytical accuracy and precision tests of the method
标准物质
编号名称 Hg标准值
(ng/g)W测定值
(ng/g)干扰扣除前Hg测定结果 干扰扣除后Hg测定结果 测定值
(ng/g)相对误差
(%)RSD
(%)测定值
(ng/g)相对误差
(%)RSD
(%)SRM 1573a 西红柿叶 34.1±1.5 3.9 33.2 −2.7 1.9 33 −3.2 1.9 GBW10047 胡萝卜 3.2±0.8 14.0 3.9 21.0 5.8 3.2 1.3 6.6 GBW10018 鸡肉 3.6±1.5 8.4 3.9 9.4 6.0 3.6 −1.1 6.7 GBW10028 黄芪 (12) 297 25.1 109.0 3.2 11.7 −2.3 5.9 GBW10049 大葱 12.0±2.3 19.9 14.2 18.3 3.5 13.3 10.9 2.6 GBW10025 螺旋藻 (15) 332 30.9 105.8 2.4 15.9 6.1 3.8 GBW10015a 菠菜 21±5 317 34.4 63.8 5.0 21.7 3.4 7.0 GBW10020 柑橘叶 150±20 96.8 154.3 2.9 0.7 149.9 0.0 0.7 GBW07601a 人发 670±100 32.2 700.1 4.5 2.1 698.7 4.3 2.1 注：括号内的数据为参考值，Hg标准值主要为原子荧光光谱法定值数据。
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