Determination of Silicon in Soil and Sediment by ICP-OES with Rapid Ultrasonic Digestion
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摘要:
利用电感耦合等离子体发射光谱法(ICP-OES)分析土壤和沉积物中硅元素的含量，样品分解方法多采用酸溶法和熔融法。硅在浓酸溶液中与氢氟酸反应形成易挥发的四氟化硅，加热造成硅的损失。熔融法可以处理土壤和沉积物样品，但会引入大量的盐，基体效应较大、检出限高。本文建立了超声密闭酸溶，ICP-OES测定土壤和沉积物中硅含量的方法。样品经稀王水、氢氟酸和双氧水在超声仪中密闭消解、定容稀释后，用配备耐氢氟酸进样系统的ICP-OES进行测定。测试时，选取251.611nm为硅的分析谱线，标准曲线在5～50mg/L范围的相关系数大于0.99997，方法检出限为0.0395mg/g。采用本方法测定不同类型土壤和沉积物标准物质，测定结果的相对标准偏差(RSD)在 0.26%～0.54%，相对误差在−0.28%～0.25%；实际样品的RSD在0.52%～0.77%。经国家标准物质GBW07401a、GBW07405a、GBW07377、GBW07379验证，硅元素的测定值与标准值一致；同时用X射线荧光光谱法测定这四种国家标准物质中的硅含量，两种方法的分析结果基本相符。
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关键词:
- 硅 /
- 土壤；沉积物 /
- 超声封闭消解 /
- 电感耦合等离子体发射光谱法
Abstract:The literature provides references for the accurate determination of silicon content in soil and sediment by inductively coupled plasma-optical emission spectrometry (ICP-OES). Sample decomposition methods often use acid dissolution or melting methods. Silicon reacts with hydrofluoric acid in concentrated acid solution to form volatile silicon tetrafluoride, which is lost due to heating. The melting method can process soil and sediment samples, but it introduces a large amount of salt, a significant matrix effect and high detection limit. This article describes a method for determining silicon content in soil and sediment using ultrasonic sealed acid dissolution and ICP-OES. After the sample was dissolved in dilute aqua regia, hydrofluoric acid, and hydrogen peroxide in an ultrasonic apparatus and diluted to a constant volume, the sample was measured using ICP-OES equipped with a hydrofluoric acid resistant injection system. During ICP-OES testing, 251.611nm was selected as the analytical spectral line for silicon. The correlation coefficient of the standard curve in the range of 5mg/L to 50mg/L was greater than 0.99997, and the detection limit of the method was 0.0395mg/g. This method was used to test different types of soil and sediment standard substances, with relative standard deviations (RSD) ranging from 0.26% to 0.54% and relative errors ranging from −0.28%−0.25%. The actual sample testing RSD range from 0.52% to 0.77%. Verified by national standard substances GBW07401a, GBW07405a, GBW07377, and GBW07379, the measured values of silicon element were consistent with the standard values. At the same time, X-ray fluorescence spectrometry was used to determine the silicon content in these four national standard substances, and the results were consistent.
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表 1 不同消解条件下样品测试结果的比较
Table 1. Comparison of results with different digestion conditions
序号 实验条件 SiO2含量测定值
(%)RSD
(%)以SiO2计平均值
(%)SiO2含量认定值及
不确定度(%)以SiO2计相对误差
(%)1 静置 39.86 39.90 40.26 0.6 40.01 56.60±0.46 −29.31 2 75℃加热 51.13 51.34 50.92 0.4 51.13 56.60±0.46 −9.67 3 75℃超声 57.29 56.41 55.71 1.4 56.47 56.60±0.46 −0.23 
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表 2 密闭条件对样品消解效果的影响
Table 2. Influence of different sealing conditions on sample digestion
序号 密闭方式 SiO2含量测定值
(%)RSD
(%)以SiO2计平均值
(%)SiO2含量认定值和
不确定度(%)以SiO2计相对误差
(%)1 敞口 49.14 49.14 48.84 0.3 49.04 56.60±0.46 −13.36 2 半密封 51.07 50.92 50.02 1.1 50.67 56.60±0.46 −10.48 3 密闭 57.29 56.41 55.71 1.4 56.47 56.60±0.46 −0.23
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表 3 超声温度对样品消解效果的比较
Table 3. Comparison of results with different ultrasound temperature
序号 超声温度
(℃)SiO2含量测定值
(%)RSD
(%)Si含量平均值
(%)以SiO2计平均值
(%)SiO2含量认定值和
不确定度(%)以SiO2计相对误差
(%)1 25 40.48 40.82 40.82 0.5 19.03 40.71 56.60±0.46 −28.07 2 45 45.59 45.46 44.88 0.8 21.18 45.31 56.60±0.46 −19.95 3 75 57.29 56.41 55.71 1.4 26.40 56.47 56.60±0.46 −0.23 4 85 55.45 56.71 56.18 1.1 26.23 56.11 56.60±0.46 −0.87
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表 4 超声时间对样品前处理效果的比较
Table 4. Comparison of results with different ultrasound time
序号 超声时间
(h)SiO2含量测定值
(%)RSD
(%)Si含量平均值
(%)以SiO2计平均值
(%)SiO2含量认定值和
不确定度(%)以SiO2计相对误差
(%)1 0.5 50.34 49.68 50.38 0.8 23.43 50.13 56.60±0.46 −11.43 2 1 57.29 56.41 55.71 1.4 26.40 56.47 56.60±0.46 −0.23 3 2 57.08 57.10 56.22 0.9 26.55 56.80 56.60±0.46 0.35 4 3 56.26 56.50 56.29 0.2 26.34 56.35 56.60±0.46 −0.44
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表 5 超声功率对样品前处理效果的测试结果比较
Table 5. Comparison of results with different ultrasound powder
序号 超声条件 Si含量测定值
（%）RSD
（%）Si含量测定平均值
(%)以SiO2计平均值
（%）SiO2含量认定值
及不确定度（%）以SiO2计相对误差
（%）1 75℃超声功率120W 56.44 55.64 55.39 1.0 26.09 55.82 56.60±0.46 −1.38 2 75℃超声功率240W 55.90 55.97 55.75 0.3 26.10 55.87 56.60±0.46 −1.29 3 75℃超声功率300W 57.29 56.41 55.71 1.4 26.40 56.47 56.60±0.46 −0.23 4 75℃超声功率360W 56.50 56.95 56.97 0.5 26.55 56.80 56.60±0.46 0.35
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表 6 不同添加量的双氧水对样品进行消解测试结果比较
Table 6. Comparison of results with different amounts of hydrogen peroxide added
序号 双氧水用量
（mL）Si含量测定值
（%）RSD
（%）Si含量测定平均值
(%)以SiO2计平均值
（%）SiO2含量认定值
及不确定度（%）以SiO2计相对误差
（%）1 0 42.89 42.25 42.44 0.8 19.88 42.53 56.60±0.46 −24.86 2 3 50.30 48.97 48.50 1.9 23.02 49.26 56.60±0.46 −12.97 3 6 57.29 56.41 55.71 1.4 26.40 56.47 56.60±0.46 −0.23 4 9 55.92 55.73 56.78 1.0 26.24 56.14 56.60±0.46 −0.81
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表 7 方法精密度和准确度实验
Table 7. Precision and accuracy tests of the method
标准物质编号 Si含量测定值
(%)RSD
(%)Si含量测定
平均值(%)以SiO2计
平均值（%）SiO2含量认定值
及不确定度（%）以SiO2计
相对误差（%）GBW07401a 56.91 56.80 56.84 0.40 26.52 56.74 56.60±0.46 0.25 56.22 56.93 56.65 56.99 56.71 56.91 56.69 56.50 GBW07405a 61.48 61.18 61.81 0.31 28.68 61.35 61.52±0.39 −0.28 61.16 61.33 61.25 61.21 61.21 61.44 61.36 61.38 GBW07377 63.50 63.17 63.75 0.26 29.65 63.43 63.48±0.43 −0.08 63.52 63.47 63.43 63.35 63.28 63.56 63.24 63.50 GBW07379 69.38 69.98 69.21 0.54 32.62 69.75 69.66±0.6 0.13 70.15 69.79 70.08 69.87 70.17 69.76 69.12 69.70
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表 8 实际样品测试结果比对
Table 8. Comparison of analytical results of SiO2 content in actual samples
实际样品编号 本文方法Si含量测定值
(%)RSD
（%）Si含量测定平均值
(%)XRF法Si含量测定值
(%)相对误差
(%)样品8 29.98 29.72 30.18 29.68 29.90 0.68 29.89 26.12 −12.60 样品18 12.13 12.03 12.22 12.04 12.06 0.66 12.10 15.38 27.10 样品23 14.91 15.11 14.95 14.93 15.17 0.77 15.01 17.07 13.70 样品28 29.93 29.75 29.80 29.86 30.15 0.52 29.90 27.67 −7.46 样品31 31.81 31.65 31.96 31.66 31.54 0.52 31.72 29.28 −7.69
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表 9 标准物质测试结果比对
Table 9. Comparison of analytical results of SiO2 content in national standard substances
标准物质编号 本文方法Si含量
测定平均值(%)RSD
（%）XRF法Si含量
测定值(%)以SiO2计XRF法
测定值(%)SiO2含量认定值
及不确定度（%）以SiO2计本文方法与
XRF法相对误差(%)GBW07401a 26.52 0.40 27.69 59.24 56.60±0.46 4.66 GBW07405a 28.68 0.31 28.57 61.12 61.52±0.39 −0.65 GBW07377 29.65 0.26 31.10 66.53 63.48±0.43 4.80 GBW07379 32.62 0.54 33.17 70.96 69.66±0.6 1.87
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