Speciation Analysis of Inorganic Selenium in Soil by High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry
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摘要: 土壤样品中亚硒酸盐Se（Ⅳ）和硒酸盐Se（Ⅵ）的形态分析中，提取剂的选择和检测方法是技术的关键。以往的提取剂容易导致硒形态发生转变或无法同时提取Se（Ⅳ）和Se（Ⅵ），常用的氢化物发生原子荧光光谱法无法直接测定Se（Ⅵ），而是通过差减法得出Se（Ⅵ）含量。本文对比了不同提取剂的提取能力，确定使用0.1 mol/L氢氧化钠溶液作为提取剂，在55℃超声萃取土壤样品30 min，提取液经高效液相色谱分离，电感耦合等离子体质谱检测，建立了土壤中Se（Ⅳ）和Se（Ⅵ）的形态分析方法。采用Hamilton PRP X-100色谱柱，以6 mmol/L柠檬酸为流动相，pH=5.5，在8 min内可完全分离Se（Ⅳ）和Se（Ⅵ），两者的检出限分别为0.15 μg/L、0.16 μg/L，线性相关系数（r2）均大于0.999。以土壤为基体进行加标回收试验，Se（Ⅳ）和Se（Ⅵ）的回收率在84.2%~95.8%之间，相对标准偏差为1.4%~5.3%（n=6）。该方法简单快速，具有良好的精密度和准确度，适用于土壤中无机硒的形态分析。
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关键词:
- 土壤 /
- 亚硒酸盐 /
- 硒酸盐 /
- 氢氧化钠 /
- 高效液相色谱-电感耦合等离子体质谱法
Abstract:BACKGROUNDIn the speciation analysis of selenite Se (Ⅳ) and selenite Se (Ⅵ) in soil samples, the key problem is to select the extraction agents and detection methods. In the past, extraction agents may lead to Se species redistribution or cannot extract both Se (Ⅳ) and Se (Ⅵ). Selenium speciation has been routinely determined by Hydride Generation-Atomic Absorption Spectrometry (HG-AAS). However, Se (Ⅵ) cannot be directly measured and its concentration is calculated by the difference between analyzed total Se and Se (Ⅳ) concentrations. OBJECTIVESIn order to establish an analysis method for the determination of Se (Ⅳ) and Se (Ⅵ) in soil samples by selecting the appropriate extraction agent and determination technique. METHODSThe extraction capacity of different extraction agents was compared and 0.1 mol/L sodium hydroxide was selected for the experiment. Selenium species were quantitatively extracted in a ultrasonic field at 55℃ for 30 min. An analytical method for determination of Se (Ⅳ) and Se (Ⅵ) by High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS) was established. RESULTSThe results show that Se (Ⅳ) and Se (Ⅵ) can be separated within 8 min by using a Hamilton PRP X-100 reversed-phase anion exchange column with 6 mol/L citric acid as mobile phase under pH of 5.5. The detection limits of Se (Ⅳ) and Se (Ⅵ) are 0.15 μg/L and 0.16 μg/L, respectively. Linear correlation coefficient (r2) is more than 0.999, the recoveries are 84.2%-95.8%, and the relative standard deviations are 1.4%-5.3% (n=6). CONCLUSIONSThe proposed method is simple and fast and has good accuracy and high precision, which meets the requirements for analyzing inorganic selenium in soil. -
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表 1 使用不同提取剂提取土壤中硒形态分析结果
Table 1. Analytical results of selenium species in soil extracted with different agents
土壤样品 硒形态 提取剂 超纯水 柠檬酸 磷酸盐溶液 碳酸氢钠 氢氧化钠 土壤1 Se(Ⅳ)含量(mg/kg) ND ND 0.055 0.029 0.135 Se(Ⅵ)含量(mg/kg) ND ND ND ND 0.038 硒形态总量(mg/kg) - - 0.055 0.029 0.173 总硒(mg/kg) 0.302 0.302 0.302 0.302 0.302 硒提取率(%) - - 18.21 9.6 57.28 Se(Ⅳ)含量(mg/kg) ND ND 0.154 0.122 0.206 Se(Ⅵ)含量(mg/kg) ND ND ND ND 0.078 土壤2 硒形态总量(mg/kg) - - 0.154 0.122 0.284 总硒(mg/kg) 0.362 0.362 0.362 0.362 0.362 硒提取率(%) - - 42.54 33.70 78.49 Se(Ⅳ)含量(mg/kg) ND ND 0.063 0.035 0.118 Se(Ⅵ)含量(mg/kg) ND ND ND ND 0.022 土壤3 硒形态总量(mg/kg) - - 0.063 0.035 0.140 总硒(mg/kg) 0.218 0.218 0.218 0.218 0.218 硒提取率(%) - - 28.90 16.06 64.19 注：ND表示未检出。 
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表 2 Se(Ⅳ)和Se(Ⅵ)的线性范围、检出限和加标回收试验
Table 2. Linear ranges, detection limits and spiked recoveries of Se(Ⅳ) and Se(Ⅵ)
硒形态 线性范围(μg/L) 线性方程 相关系数(r2) 方法检出限(μg/L) 加标回收率试验(n=6) 标准加入量(mg/kg) 测定值(mg/kg) 回收率(%) RSD(%) 0 0.135 - - Se(Ⅳ) 0.5~500 y=667.2x+843.8 0.9996 0.15 0.100 0.223 87.7 2.5 0.200 0.322 93.4 1.4 0 0.038 - - Se(Ⅵ) 0.5~500 y=685.4x-233.0 0.9997 0.16 0.020 0.080 84.2 5.3 0.050 0.134 95.8 4.2
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表 3 样品分析结果
Table 3. Analytical results of the sample
样品编号 Se(Ⅳ)含量(mg/kg) Se(Ⅵ)含量
(mg/kg)硒形态总量
(mg/kg)总硒
(mg/kg)硒提取率
(%)1 0.028 0.016 0.045 0.239 18.68 2 0.048 0.024 0.072 0.330 21.77 3 0.041 0.015 0.056 0.123 45.17 4 0.082 0.040 0.122 0.159 76.51 5 0.048 0.018 0.066 0.164 40.29 6 0.306 0.077 0.384 0.646 59.37 7 0.433 0.032 0.465 0.762 61.03 8 0.158 0.039 0.197 0.346 57.04 9 0.047 0.020 0.067 0.101 65.97 10 0.049 0.019 0.068 0.112 60.96 11 0.192 0.067 0.259 0.360 71.82 12 0.283 0.092 0.375 0.502 74.73 13 0.057 0.021 0.078 0.160 48.70 14 0.044 0.018 0.062 0.127 48.49 15 0.057 0.019 0.076 0.165 46.14 16 0.066 0.036 0.101 0.214 47.40 17 0.087 0.027 0.114 0.230 49.65 18 0.060 0.021 0.081 0.168 48.39 19 0.118 0.022 0.140 0.218 64.19 20 0.058 0.028 0.085 0.221 38.52 21 0.170 0.033 0.203 0.247 82.06 22 0.050 0.016 0.066 0.088 74.60 23 0.076 0.031 0.107 0.217 49.30 24 0.055 0.023 0.077 0.148 52.36 25 0.206 0.078 0.284 0.362 78.49
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