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为精准快速测定海洋生物体中砷(As)和硒(Se)含量，本研究针对海洋生物体复杂基体带来的质谱干扰、基体效应等问题，建立了基于ICP-MS/MS的分析方法。研究优化了有机溶剂增敏剂、分析模式、氧气流量等关键参数，确定4%异丙醇为最佳增敏剂，选用TQ-O2反应模式并设置氧气流量0.3 mL/min，同时筛选锗(Ge)作为内标元素校正基体效应，有效消除质谱干扰和基体干扰并提升检测灵敏度。方法验证结果显示，As和Se的标准曲线相关系数均大于0.999 8，方法检出限分别低至0.001和0.003 mg/kg，显著优于标准GB 17378.6—2007检出限(砷0.2 mg/kg、硒0.2 mg/kg)。对标准物质测定的相对标准偏差(RSD)≤5.7%，相对误差(RE)处于-2.7%～7.9%，精密度与正确度良好。实际样品测定及方法比对表明，该方法与原子荧光光谱法的测定结果无显著性差异(n=6时，t值均小于1.812,F值均小于5.05)，适用于各类海洋生物体样品的砷、硒检测。
Abstract：To accurately and rapidly determine arsenic(As) and selenium(Se) contents in marine organisms,this study established an analytical method based on inductively coupled plasma-tandem mass spectrometry(ICP-MS/MS) to address mass spectral interference and matrix effects caused by the complex matrix of marine biological samples. Marine organisms contain various complex components,which easily induce severe matrix effects and affect detection accuracy and sensitivity. Therefore,optimizing experimental parameters and eliminating interference factors are crucial to improving the reliability and stability of the analytical method. Key experimental parameters,including organic solvent sensitizer,analytical mode and oxygen flow rate,were systematically optimized through a series of conditional experiments. 4% isopropanol was confirmed as the optimal organic solvent sensitizer,which could effectively enhance the signal intensity of As and Se and improve detection sensitivity. The triple-quadrupole oxygen reaction mode(TQ-O2) was selected,and the oxygen flow rate was set at 0. 3 mL/min to eliminate polyatomic ion interference. Meanwhile,germanium(Ge) was screened as the internal standard element to correct matrix effects,further ensuring the accuracy of determination results. Method validation results showed that the correlation coefficients( of the standard curves for As and Se were both greater than 0. 999 8,indicating an excellent linear relationship. The limits of detection(LOD) of the method were 0. 001 mg/kg for As and 0. 003 mg/kg for Se,which were significantly lower than the detection limits specified in the national standard GB 17378. 6— 2007(0. 2 mg/kg for both As and Se). For the determination of certified reference materials,the relative standard deviation(RSD) was ≤5. 7%,and the relative error(RE) ranged from-2. 7% to 7. 9%,meeting the requirements of analytical chemistry for precision and accuracy. Actual sample determination and method comparison experiments indicated that there was no significant difference between the proposed ICP-MS/MS method and the traditional atomic fluorescence spectrometry(AFS). When the sample size n=6,the t-values of both As and Se were less than 1. 812,and the F-values were less than 5. 05,which passed the statistical significance test. In conclusion,this method is accurate,sensitive and stable,and is suitable for the quantitative detection of As and Se in various marine biological samples.
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基本信息:
DOI：10.20236/j.CJIAC.2026.09.005
中图分类号:X835;O657.63
引用信息:
[1]徐丽芝,黄薇,张临,等.氧气动态反应-三重四极杆-电感耦合等离子体串联质谱（ICP-MS/MS）法测定海洋生物体中砷和硒[J].中国无机分析化学,2026,16(09):1613-1621.DOI:10.20236/j.CJIAC.2026.09.005.
基金信息:
海南省自然科学基金资助项目(423QN316); 国家自然科学基金青年项目(52106229)~~
2026-06-01
2026-06-01
2026-06-01