Determination of Silver in Regional Geochemical Samples by Inductively Coupled Plasma-Mass Spectrometry with Mixed Acids Digestion
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摘要:
建立了应用电感耦合等离子体质谱法(ICP-MS)分析地球化学样品中痕量银的方法，探究在动能歧视模式(KED)下，分别通入不同流速碰撞/反应气体(He)的干扰消除效果。Ag的两个稳定同位素因受到锆、铌氧化物(90Zr16O1H、91Zr16O、92Zr16O1H、93Nb16O)等的质谱干扰，对于干扰元素锆、铌含量较高而银含量低的样品，即使采用干扰系数校正也存在较大误差。结果表明：在KED模式下，通过加大氦气流速至7.0mL/min，基体元素如锆、铌氧化物产率降低，基本上消除了锆、铌氧化物对痕量Ag的多原子离子干扰。本文采用混合酸(硝酸-氢氟酸-高氯酸)敞开酸溶消解样品，残渣用王水复溶提取，结合KED模式选出干扰较小的同位素109Ag作为测定同位素，以103Rh作为内标校正基体干扰和仪器信号漂移。经国家一级标准物质验证，分析结果在标准值的允许误差范围内，方法的检出限(3SD)为0.005µg/g，测定结果的相对标准偏差(RSD，n=12)为1.43%～11.22%，满足地质矿产实验室测试质量管理规范(DZ/T 0130.4—2006)对精密度的要求。本方法适用于土壤、水系沉积物、岩石等区域地球化学样品中痕量银的分析。
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关键词:
- 酸溶 /
- 电感耦合等离子体质谱法 /
- 区域地球化学样品 /
- 痕量银 /
- KED模式
Abstract:There exists much error during determination of trace silver in geochemical samples by traditional inductively coupled plasma-mass spectrometry (ICP-MS) due to the interference of zirconium (Zr) and niobium (Nb) oxides. To eliminate the disturbance, a simple and accurate method combining mixed acid digestion and ICP-MS was built, in which the effect of He flow rate under kinetic energy discrimination (KED) mode was also investigated. Specifically, the samples were firstly digested by mixed nitric-hydrofluoric-perchloric acids. Then, the internal standard 103Rh was added into the test sample after nitrohydrochloric acid extraction to correct matrix interference and instrument signal drift. To further eliminate the interference of Zr and Nb oxides on Ag, the He flow of the collision pool was increased to 7.0mL/min, thus significantly reducing the mass spectrum interference of silver without deterioration of the signal-background ratio. Verified by national first grade reference materials, the analysis results were within the allowable range of the standard value. The detection limit (3SD) of the method was 0.005g/g with the relative standard deviation of 1.43%−11.22% (n=12). This method is suitable for the analysis of silver in regional geochemical samples such as soil, stream sediments and rocks.
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表 1 混合酸消解结合ICP-MS法分析标准物质中银含量的精密度测试结果
Table 1. The precision test results for Ag analysis in standard samples using mixed acids digestion-ICP-MS
标准物质编号 银含量(µg/g) RSD
(%)12次分次测定值 平均值 GBW07105
(岩石)0.038 0.045 0.039 0.045 0.041 11.22 0.035 0.034 0.041 0.046 0.034 0.042 0.046 0.041 GBW07402
(土壤)0.052 0.051 0.053 0.049 0.052 6.32 0.055 0.051 0.050 0.048 0.047 0.053 0.058 0.057 GBW07307a
(水系沉积物)1.212 1.221 1.195 1.187 1.202 1.43 1.182 1.175 1.222 1.221 1.218 1.210 1.195 1.186 
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表 2 混合酸消解结合ICP-MS法分析标准物质中银含量的准确度测试结果
Table 2. The accuracy test results for Ag analysis in standard samples using mixed acids digestion-ICP-MS method
标准物质类型 标准物质编号 银含量(µg/g) ∆logC 标准值 测定平均值 土壤 GBW07401 0.35±0.05 0.370 0.024 GBW07402 0.054±0.007 0.049 −0.042 GBW07403 0.091±0.007 0.086 −0.025 GBW07404 0.070±0.011 0.065 −0.032 GBW07405 4.4±0.4 4.334 −0.007 GBW07406 0.20±0.02 0.216 0.033 水系沉积物 GBW07307a 1.20±0.08 1.212 0.004 GBW07308a 0.12±0.02 0.118 −0.007 GBW07358 0.14±0.01 0.141 0.003 GBW07360 0.74±0.14 0.747 0.004 GBW07362 0.092±0.005 0.091 −0.005 GBW07363 0.082±0.008 0.081 −0.005 岩石 GBW07105 0.040±0.008 0.0447 0.048 GBW07107 0.047±0.009 0.052 0.044
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表 3 驻留时间对测试精密度的影响
Table 3. Influence of dwell time on the precision of measurement
驻留时间
(s)银含量(µg/g) RSD
(%)8次分次测定值 平均值 0.01 0.123 0.126 0.119 0.120 0.124 3.14 0.125 0.131 0.121 0.125 0.03 0.125 0.127 0.127 0.13 0.127 2.24 0.129 0.121 0.125 0.128 0.05 0.126 0.123 0.125 0.119 0.124 1.93 0.126 0.126 0.124 0.123 0.10 0.130 0.128 0.130 0.128 0.128 1.76 0.125 0.128 0.126 0.132 0.20 0.122 0.126 0.119 0.120 0.120 2.59 0.119 0.121 0.121 0.115
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表 4 稀释体积对含离线内标的样品溶液测定精密度的影响
Table 4. Influence of dilution volume on the precision determination for the sample solution containing off-line internal standard material
含内标的样品
溶液稀酸的
加入量
(mL)稀释后
体积
(mL)内标
回收率
(%)银含量
测定值
(μg/g)RSD
(%)2.21µg/g测定液
(1.0mL)9.0 10.0 96.0 2.216 1.26 9.2 10.2 95.2 2.181 9.8 10.8 87.0 2.213 10.1 11.1 84.8 2.222 10.7 11.7 80.8 2.245 11.0 12.0 75.7 2.262 0.54µg/g测定液
(1.0mL)9.0 10.0 95.9 0.538 1.48 9.2 10.2 91.3 0.537 9.8 10.8 87.7 0.540 10.1 11.1 83.0 0.535 10.7 11.7 77.3 0.557 11.0 12.0 75.0 0.544
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表 5 不同实验室利用混合酸消解结合ICP-MS法测试实际样品的分析结果对比
Table 5. Comparison of the analysis results for actual samples using mixed acids digestion-ICP-MS method in different laboratories
样品编号 银含量测定值(µg/g) 相对偏差绝对值
(%)实验室1 实验室2 样品-1 0.137 0.140 2.17 样品-2 0.061 0.066 7.87 样品-3 0.057 0.052 9.17 样品-4 0.067 0.065 3.03 样品-5 0.062 0.066 6.25 样品-6 0.086 0.089 3.43 样品-7 0.082 0.090 9.30 样品-8 0.087 0.088 1.14 样品-9 0.072 0.076 5.41 样品-10 0.114 0.099 14.1
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表 6 混合酸消解结合ICP-MS法和发射光谱法测试结果对比
Table 6. Comparison of the determination results between the mixed acids digestion-ICP-MS method and emission spectroscopy method
样品编号 银含量测定值(µg/g) 相对偏差
d(%)双侧检验
t本文方法
测定值发射光谱法
测定值样品1 0.062 0.066 −6.25 1.30 样品2 0.066 0.063 4.65 样品3 0.055 0.052 5.61 样品4 0.057 0.054 5.41 样品5 0.060 0.054 10.5 样品6 0.058 0.061 −5.04 样品7 0.063 0.059 6.56
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