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    固相萃取-电感耦合等离子体质谱法测定硒强化婴幼儿配方食品中无机硒和有机硒的含量

    Determination of Inorganic Selenium and Organic Selenium in Selenium Fortified Infant Formula Foods by Inductively Coupled Plasma Mass Spectrometry with Solid Phase Extraction

    • 摘要: 采用固相萃取-电感耦合等离子体质谱法(ICP-MS)测定硒强化婴幼儿配方食品中无机硒和总硒的含量,并通过差减法计算有机硒含量。对于样品中总硒的测定,取0.500 0 g样品置于消解罐中,加入5 mL硝酸,于185 ℃消解20 min,于120 ℃赶酸至近干,冷却后用0.3 mol·L−1盐酸溶液定容至50 mL;对于样品中无机硒的测定,取1.000 0 g样品置于50 mL离心管中,加入40.0 mL水,涡旋振荡10 min,超声10 min,加入3%(体积分数)乙酸溶液0.4 mL,摇匀,静置,待沉淀完毕后,离心10 min,取5.0 mL上清液,用5 g·L−1氢氧化钠溶液调节pH至5~7,转移至活化后的Oasis WAX固相萃取柱上,用5 mL水淋洗,5 mL 0.3 mol·L−1盐酸溶液洗脱,收集洗脱液。上述溶液分别在氧气反应模式下采用ICP-MS测定,在线加入1 mg·L−1锗内标溶液。结果显示,无机硒的质量浓度在0.5~10 μg·L−1内和对应的信号响应强度与内标信号响应强度的比值呈线性关系,检出限(3s)为0.1 μg·(100 g)−1。按照标准加入法进行回收试验,回收率为91.0%~97.0%,测定值的相对标准偏差(n=6)为2.0%~2.4%。方法用于分析14份硒强化婴幼儿配方食品样品,硒主要以有机形态存在,其中特殊医学用途硒强化婴幼儿配方食品中无机硒的占比高于10.00%,低于14.00%,普通硒强化婴幼儿配方食品中无机硒的占比低于6.00%。

       

      Abstract: A method for the determination of inorganic selenium and total selenium in selenium fortified infant formula foods by inductively coupled plasma mass spectrometry (ICP-MS) with solid phase extraction was proposed, and the determination of organic selenium was calculated by the subtraction method. For the determination of total selenium in the sample, 0.5000 g of sample was taken and placed in a digestion tank, and 5 mL of nitric acid was added. The mixture was digested at 185 ℃ for 20 min, the acid was driven off at 120 ℃ until the solution was evaporated to near dryness. After cooling, the mixture was made its volume up to 50 mL with 0.3 mol·L−1 hydrochloric acid solution. For the determination of inorganic selenium in the sample, 1.000 0 g of sample was taken and placed in a 50 mL-centrifuge tube, and 40.0 mL of water was added. The mixture was vortexed for 10 min and sonicated for 10 min, and 0.4 mL of 3% (volume fraction) acetic acid solution was added. The solution was shaken well and settled, and after precipitation, the mixture was centrifugated for 10 min. 5.0 mL of supernatant was taken, and the pH was adjusted to 5‒7 with 5 g·L−1 sodium hydroxide solution, and the solution was transferred to an activated Oasis WAX solid phase extraction column. It was rinsed with 5 mL of water, elution was performed with 5 mL of 0.3 mol·L−1 hydrochloric acid solution, and the eluate was collected. Determination was performed by ICP-MS in the condition of oxygen reaction mode, and 1 mg·L−1 germanium internal standard solution was added online. As shown by the results, linear relationship between the ratios of the corresponding signal response intensity to the internal standard signal response intensity and mass concentrations of the inorganic selenium was kept in the range of 0.5‒10 μg·L−1, and the detection limit (3s) was 0.1 μg·(100 g)−1. Test for recovery was made by the standard addition method, giving results in the range of 91.0%‒97.0%, with RSDs (n=6) of the determined values in the range of 2.0%‒2.4%. This method was applied to the analysis of 14 selenium fortified infant formula food samples, and selenium was mainly presented in organic form. Among them, the proportion of inorganic selenium in selenium fortified infant formula food for special medical purposes was higher than 10.00% and lower than 14.00%, while the proportion of inorganic selenium in ordinary selenium fortified infant formula food was lower than 6.00%.

       

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