Determination of Rare Earth Elements in Soil and Stream Sediment by Inductively Coupled Plasma-Mass Spectrometry with Automatic Graphite Digestion
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摘要:
稀土元素由于化学性质稳定，均一化程度高，常作为地球化学示踪剂，为揭示岩石、矿物成因、成岩成矿的地球化学条件以及物质来源和岩浆分异演化等提供重要信息，因此，建立快速、准确地测定地质样品中稀土元素含量的方法非常重要。地质样品因基体复杂，大部分的样品前处理需要酸溶，酸溶试剂用量大，溶样过程中产生的酸雾易对实验人员造成伤害，且批量样品前处理劳动强度大。基于此，本文建立了以全自动石墨消解仪消解样品，“加酸—消解—赶酸—定容—摇匀”全程用软件控制，以Rh和Re为内标，电感耦合等离子体质谱法（ICP-MS）测定土壤和水系沉积物中La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y等15个稀土元素的方法。通过12个土壤和水系沉积物国家一级标准物质对消解程序、消解混合酸及方法精密度、准确度和检出限进行研究。结果表明：按照优化后的消解程序消解土壤和水系沉积物，混合酸用量为4mL，稀土各元素测定值与标准值一致，相对误差（RE）绝对值在0～6.67%之间，ΔlgC绝对值在0～0.028之间，相对标准偏差（RSD）在0.97%～4.62%之间。全自动石墨消解因自动化操作，操作条件一致，温度均匀，精度更高，各元素的RSD值均小于电热板消解的元素RSD值。本方法精密度、准确度和检出限满足《地质矿产实验室测试质量管理规范》的要求，混合酸用量远低于常用的电热板消解法，相应的环境污染也减少；方法精密度优于常用的电热板消解法。前处理时只需要称样后将消解管置于石墨消解仪中，溶样全过程自动完成，自动化程度高，适用于批量样品的测试。
Abstract:BACKGROUND Rare earth elements were used as geochemical tracers usually to provide important information for revealing the genesis of rocks and minerals, geochemical conditions of diagenesis and mineralization, material sources and magmatic differentiation and evolution, due to their stable chemical properties and high degree of uniformity. Therefore, it was very important to develop a method for rapidly and accurately determining the contents of rare earth elements in geological samples. In addition, due to the complex matrix of geological samples, most samples needed to be acid-dissolved in pre-treatment, and the amount of acid-dissolved reagents was large. The acid mist generated in the process of sample dissolution was harmful to the experimental personnel and the labor intensity of batch sample pretreatment was high.
OBJECTIVES To establish a rapid and accurate method for batch determination of rare earth elements in geological samples.
METHODS A method was developed to measure 15 rare earth elements such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y in soil and stream sediment by inductively coupled plasma-mass spectrometry with Rh and Re as the internal standard, in which the pre-treatment process of “acid addition—digestion—acid removal—constant volume—shaking” was controlled by software and completed with an automatic graphite digestion instrument. The digestion procedure, the effects of digestion mixed acid, precision, accuracy, and detection limit of the method were studied by soil and stream sediment reference materials including GBW07402, GBW07446, GBW07448, GBW07454, GBW07456, GBW07457, GBW07304a, GBW07307a, GBW07308, GBW07312, GBW07359 and GBW07361.
RESULTS The results showed that the amount of mixed acids was 4mL consumed by soil and stream sediment digestion according to optimized digestion procedure. The absolute values of relative error and ΔlgC of rare earth elements were 0-6.67% and 0-0.028, respectively. Therefore, the measured values were consistent with certified values. The relative standard deviation (RSD) of rare earth elements was 0.97%-4.62%, which is lower than the RSD of the electric plate digestion method.
CONCLUSIONS The precision, accuracy and detection limit of the method meet the requirements of the specification of testing quality management for geological laboratories-part 4 “Analysis methods for regional geochemical sample”. The precision of the method is better than electric plate digestion method. The amount of mixed acid used in the method is 4mL, which is much lower than that in the electric plate digestion method, the corresponding environmental pollution is also reduced. The detection limit of most rare earth elements in the method is lower than that in the standard method. The pre-processing of the automatic digestion method only requires the experimental personnel to weigh the sample and place it in the digestion tube in the automatic graphite digestion instrument and the whole process of dissolution is then automated. The automation degree is high, which guarantees the safety of experimental personnel to the greatest extent and can be applied to the testing of batch samples.
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表 1 电感耦合等离子体质谱仪工作条件
Table 1. Operating parameters for ICP-MS measurements.
ICP-MS工作参数 实验条件 ICP-MS工作参数 实验条件 射频功率 1350W 扫描方式 跳峰 雾化器流速 0.85L/min 测量点/峰 3 冷却气流速 12L/min 重复测定次数 3 辅助气流速 1.2L/min 停留时间 10ms/点 采样深度 90步 扫描次数 40 采样锥/截取锥 1.0mm/0.7mm 测量时间 60s 
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表 2 不同方法精密度结果比较
Table 2. Comparison of precision results of REEs in reference materials for different methods.
元素 GBW07448（n=12） GBW07454（n=12） 认定值
（µg/g）消解仪 电热板 认定值
（µg/g）消解仪 电热板 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） La 30±1 30.8 2.45 31.2 4.49 35±1 36.0 1.74 36.5 2.74 Ce 57±2 56.0 2.21 57.0 4.82 71±3 71.0 1.90 73.0 2.80 Pr 6.9±0.3 6.6 2.27 6.70 4.18 8.0±0.5 7.90 1.83 8.15 2.27 Nd 25±1 25.5 2.44 25.8 4.55 31±1 31.8 2.37 30.9 3.49 Sm 4.7±0.2 4.77 2.63 4.84 3.83 5.8±0.3 5.98 2.97 5.66 4.09 Eu 1.00±0.05 1.00 1.14 1.01 2.44 1.20±0.06 1.19 1.52 1.23 4.03 Gd 4.2±0.2 4.17 2.56 4.29 3.83 5.3±0.3 5.34 2.38 5.52 4.65 Tb 0.69±0.03 0.66 2.99 0.67 3.20 0.86±0.06 0.84 2.60 0.86 3.52 Dy 3.8±0.2 3.80 2.89 3.88 4.27 5.0±0.4 5.00 1.90 5.00 2.99 Ho 0.77±0.04 0.76 3.76 0.77 5.03 1.02±0.08 0.99 1.58 1.00 2.51 Er 2.2±0.2 2.15 3.90 2.11 5.13 2.8±0.3 2.66 1.69 2.68 2.31 Tm 0.35±0.03 0.34 3.98 0.34 4.52 0.46±0.04 0.47 1.99 0.44 4.68 Yb 2.2±0.2 2.15 4.27 2.14 5.96 3.3±0.3 3.20 2.21 3.16 4.67 Lu 0.35±0.02 0.34 3.61 0.36 6.97 0.45±0.04 0.47 1.79 0.43 5.28 Y 21±1 20.2 3.79 20.5 5.95 27±2 25.9 1.35 25.8 3.63 元素 GBW07456（n=12） GBW07308（n=12） 认定值
（µg/g）消解仪 电热板 认定值
（µg/g）消解仪 电热板 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） La 43±1 44.1 1.39 45.1 3.44 30±4 28.8 1.51 28.9 3.01 Ce 82±4 82.4 1.68 83.9 3.71 54±5 53.0 0.97 52.0 2.60 Pr 9.8±0.8 9.51 1.29 9.75 3.52 5.8±0.7 5.66 1.43 5.66 3.28 Nd 44±2 45.4 1.58 46.1 3.75 21±2 20.6 1.54 20.6 3.16 Sm 6.9±0.3 7.12 2.00 7.17 3.22 3.8±0.3 3.70 1.57 3.70 3.41 Eu 1.50±0.05 1.50 1.98 1.51 2.24 0.56±0.07 0.54 1.36 0.57 3.91 Gd 6.2±0.3 6.25 1.47 6.36 3.50 3.5±0.6 3.39 1.51 3.65 3.37 Tb 1.00±0.04 0.99 1.95 1.00 2.11 0.54±0.10 0.52 1.20 0.55 4.65 Dy 5.7±0.2 5.71 1.75 5.74 2.98 2.6±0.5 2.72 1.33 2.69 3.56 Ho 1.13±0.07 1.13 1.68 1.12 3.23 0.7±0.02 0.86 1.54 0.94 2.63 Er 3.2±0.2 3.13 1.55 3.07 2.95 1.8±0.3 1.72 2.37 1.78 3.63 Tm 0.51±0.03 0.49 2.17 0.49 5.48 0.33±0.06 0.32 2.25 0.34 4.00 Yb 5.8±0.5 5.66 2.05 5.61 3.48 2.1±0.3 2.04 2.53 2.03 3.79 Lu 0.50±0.02 0.48 2.15 0.49 3.04 0.38±0.07 0.37 1.46 0.37 3.11 Y 31±2 29.5 1.51 29.6 2.68 18±2 17.2 2.20 18.7 4.31 元素 GBW07359（n=12） GBW07312（n=12） 认定值
（µg/g）消解仪 电热板 认定值
（µg/g）消解仪 电热板 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） 平均值（µg/g） RSD（%） La 13.9±1.0 13.6 4.09 13.8 5.74 32.7±1.4 30.9 1.38 32.5 4.67 Ce 24±2 22.8 3.95 23.2 4.16 61±4 61.5 0.98 59.0 4.91 Pr 2.9±0.3 2.79 3.66 2.79 4.94 6.9±1.1 6.58 1.20 6.83 4.32 Nd 9.8±0.4 9.49 3.68 9.98 4.72 26±3 26.9 1.08 25.3 4.53 Sm 1.9±0.1 1.82 3.23 1.88 4.40 5±0.4 4.79 1.04 5.08 3.49 Eu 0.62±0.03 0.61 2.47 0.62 3.73 0.61±0.03 0.58 2.39 0.61 2.64 Gd 1.7±0.1 1.63 2.23 1.71 4.28 4.4±0.4 4.19 1.54 4.60 4.99 Tb 0.29±0.02 0.28 1.73 0.28 4.10 0.82±0.06 0.84 1.88 0.80 5.17 Dy 1.7±0.1 1.67 3.22 1.67 4.40 4.8±0.2 4.59 2.85 5.04 5.06 Ho 0.33±0.02 0.33 3.06 0.33 6.99 0.94±0.07 0.97 3.42 0.99 6.08 Er 0.93±0.09 0.89 3.77 0.89 5.21 3.1±0.3 2.98 1.72 3.06 5.91 Tm 0.16±0.02 0.153 3.69 0.165 6.98 0.53±0.06 0.55 1.91 0.55 5.68 Yb 1.0±0.1 1.02 3.40 1.01 5.78 3.7±0.4 3.84 2.00 3.81 5.55 Lu 0.16±0.02 0.155 4.62 0.166 6.05 0.58±0.06 0.59 2.16 0.56 5.82 Y 9.7±0.7 9.64 3.04 10.14 4.82 29±3 27.7 1.88 27.9 5.89
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表 3 方法准确度结果
Table 3. Accuracy results of REEs in reference materials by ICP-MS.
元素 GBW07402 GBW07446 认定值（µg/g） 测定值（µg/g） ΔlgC RE（%） 认定值（µg/g） 测定值（µg/g） ΔlgC RE（%） La 164±11 173 0.023 5.49 14±0.3 13.9 −0.003 −0.71 Ce 402±16 421 0.020 4.73 25±2 24.8 −0.003 −0.80 Pr 57±6 59.3 0.017 4.04 3.2±0.2 3.15 −0.007 −1.56 Nd 210±14 220 0.020 4.76 12.4±0.4 12.4 0.000 0.00 Sm 18±2 18.4 0.010 2.22 2.4±0.1 2.44 0.007 1.67 Eu 3.0±0.2 3.10 0.014 3.33 0.66±0.05 0.67 0.007 1.52 Gd 7.8±0.6 8.00 0.011 2.56 2.2±0.1 2.17 −0.006 −1.36 Tb 0.97±0.26 0.98 0.004 1.03 0.37±0.03 0.36 −0.012 −2.70 Dy 4.4±0.3 4.61 0.020 4.77 2.3±0.2 2.29 −0.002 −0.43 Ho 0.93±0.12 0.90 −0.014 −3.23 0.46±0.04 0.46 0.000 0.00 Er 2.1±0.4 2.16 0.012 2.86 1.3±0.1 1.31 0.003 0.77 Tm 0.42±0.11 0.41 −0.010 −2.38 0.23±0.02 0.22 −0.019 −4.35 Yb 2.0±0.2 2.10 0.021 5.00 1.5±0.1 1.48 −0.006 −1.33 Lu 0.32±0.05 0.31 −0.014 −3.13 0.24±0.02 0.23 −0.018 −4.17 Y 22±2 21.4 −0.012 −2.73 12.7±0.8 12.3 −0.014 −3.15 元素 GBW07304a GBW07361 认定值（µg/g） 测定值（µg/g） ΔlgC RE（%） 认定值（µg/g） 测定值（µg/g） ΔlgC RE（%） La 44±1 45.6 0.016 3.64 11.8±0.6 12.0 0.007 1.69 Ce 90±3 91.3 0.006 1.44 32±2 31.6 −0.005 −1.25 Pr 9.9±0.2 9.90 0.000 0.00 2.5±0.4 2.51 0.002 0.40 Nd 36±2 36.9 0.011 2.50 8.9±1.0 8.92 0.001 0.22 Sm 6.6±0.2 6.79 0.012 2.88 1.6±0.1 1.62 0.005 1.25 Eu 1.30±0.03 1.33 0.010 2.31 0.54±0.05 0.57 0.023 5.56 Gd 5.9±0.2 6.16 0.019 4.41 1.4±0.1 1.46 0.018 4.29 Tb 0.92±0.04 0.95 0.014 3.26 0.22±0.02 0.22 0.00 0.00 Dy 5.3±0.4 5.60 0.024 5.66 1.3±0.1 1.29 −0.003 −0.77 Ho 1.05±0.06 1.12 0.028 6.67 0.26±0.03 0.25 −0.017 −3.85 Er 3.0±0.3 3.08 0.011 2.67 0.8±0.1 0.76 −0.022 −5.00 Tm 0.50±0.03 0.49 −0.009 −2.00 0.13±0.02 0.125 −0.017 −3.85 Yb 3.2±0.3 3.20 0.000 0.00 0.83±0.04 0.81 −0.011 −2.41 Lu 0.50±0.03 0.47 −0.027 −6.00 0.14±0.03 0.135 −0.016 −3.57 Y 29±2 29.2 0.003 0.69 7.0±0.6 6.61 −0.025 −5.57
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表 4 方法检出限
Table 4. Detection limits of the method.
元素 本方法检出限
（µg/g）标准方法检出限
（µg/g）元素 本方法检出限
（µg/g）标准方法检出限
（µg/g）Y 0.04 0.03 Tb 0.02 0.03 La 0.05 0.05 Dy 0.01 0.02 Ce 0.06 0.05 Ho 0.02 0.03 Pr 0.009 0.01 Er 0.01 0.01 Nd 0.04 0.05 Tm 0.01 0.03 Sm 0.01 0.02 Yb 0.01 0.01 Eu 0.01 0.01 Lu 0.02 0.02 Gd 0.02 0.05
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表 5 全自动石墨消解仪消解程序
Table 5. Resolution program of automatic graphite digestion instrument.
步骤序号 消解程序 具体条件 步骤序号 消解程序 具体条件 1 加入试剂 2mL氢氟酸，1mL硝酸，
0.5mL高氯酸，0.5mL硫酸9 加热 230℃, 60min 2 混匀 1min 10 混匀 0.5min 3 加热 200℃ 60min 11 加热 230℃, 30min 4 混匀 0.5min 12 加入试剂 20%反王水约10mL 5 加热 210℃, 60min 13 加热 180℃, 7min 6 混匀 0.5min 14 冷却 10 min 7 加热 230℃, 60min 15 定容 水定容至50mL 8 混匀 0.5min
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表 6 不同混合酸用量时稀土元素测定结果
Table 6. Comparative data of REEs in reference materials with different amounts of mixed acid by ICP-MS.
元素 GBW0745测定的相对误差(%) GBW07307a测定的相对误差(%) 3mL 3.5mL 4mL 5mL 3mL 3.5mL 4mL 5mL La −12.56 11.00 4.60 2.78 −15.22 −7.07 5.19 0.67 Ce −15.63 10.15 3.74 3.08 −10.00 −8.08 5.37 2.96 Pr −14.67 8.45 0.91 −3.00 −16.82 −12.60 3.28 2.93 Nd −15.83 8.33 2.33 −0.42 −18.63 −12.69 5.43 2.38 Sm −13.44 10.00 2.30 −0.25 −18.00 −12.62 4.62 1.84 Eu −14.26 6.52 2.90 1.22 −14.00 −17.20 2.15 1.79 Gd −12.45 10.00 3.03 3.71 21.11 −20.00 5.29 0.86 Tb −13.85 −16.64 0.00 −2.86 −20.00 −13.25 1.92 −1.85 Dy −10.63 9.85 2.22 −0.81 −24.74 −5.29 2.41 6.54 Ho −9.62 7.90 1.57 1.30 −7.50 −10.29 1.69 −1.11 Er −11.15 −7.73 −1.08 −3.75 21.11 −8.04 −1.76 −1.11 Tm −22.56 −10.00 −3.33 −4.88 −17.50 −4.19 −3.70 −6.06 Yb −22.63 −15.74 −0.83 −5.36 21.11 −6.67 1.76 −2.86 Lu −19.76 −9.76 −5.08 −4.76 −20.53 −9.87 −3.70 −5.26 Y −12.60 −16.05 −2.35 −3.81 −17.86 −8.50 −2.50 −7.22
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表 7 土壤和水系沉积物样品测试结果
Table 7. Determination results of REEs in soil and stream sediment samples for different methods.
元素 A190350001 A190350018 标准方法(µg/g) 全自动石墨消解(µg/g) 相对偏差（%） 标准方法(µg/g) 全自动石墨消解(µg/g) 相对偏差（%） La 37.9 36.1 −4.86 16.2 17.8 9.41 Ce 68.8 69.5 1.01 27.2 29.7 8.79 Pr 7.36 6.85 −7.18 3.90 3.64 −6.90 Nd 26.8 27.5 2.58 17.1 18.2 6.23 Sm 4.46 4.20 −6.00 4.45 4.14 −7.22 Eu 1.26 1.15 −9.13 1.59 1.51 −5.16 Gd 3.84 3.94 2.57 4.28 4.67 8.72 Tb 0.53 0.57 7.27 0.72 0.79 9.27 Dy 2.40 2.33 −2.96 4.15 3.97 −4.43 Ho 0.46 0.43 −6.74 0.75 0.73 −2.70 Er 1.18 1.23 4.15 1.84 1.89 2.68 Tm 0.18 0.18 0.00 0.26 0.25 −3.92 Yb 1.15 1.11 −3.54 1.63 1.57 −3.75 Lu 0.17 0.16 −6.06 0.21 0.21 0.00 Y 10.9 11.5 5.36 16.8 17.6 4.65 元素 A221060001 A221060008 标准方法(µg/g) 全自动石墨消解(µg/g) 相对偏差（%） 标准方法(µg/g) 全自动石墨消解(µg/g) 相对偏差（%） La 44.2 45.3 2.46 34.8 33.7 −3.21 Ce 84.6 86.5 2.22 66.1 63.2 −4.49 Pr 8.93 9.18 2.76 7.16 6.97 −2.69 Nd 28.5 29.3 2.77 23.3 22.6 −3.05 Sm 5.08 5.07 −0.20 4.40 4.26 −3.23 Eu 0.84 0.80 −4.88 0.70 0.70 0.00 Gd 4.22 4.16 −1.43 3.62 3.63 0.28 Tb 0.62 0.62 0.00 0.59 0.61 3.33 Dy 3.42 3.30 −3.57 3.69 3.93 6.30 Ho 0.66 0.64 −3.08 0.76 0.82 7.59 Er 1.79 1.69 −5.75 1.96 2.13 8.31 Tm 0.28 0.26 −7.41 0.36 0.39 8.00 Yb 1.87 1.75 −6.63 2.42 2.60 7.17 Lu 0.26 0.24 −8.00 0.28 0.30 6.90 Y 18.2 16.8 −8.00 19.6 21.2 7.84
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