目的: 分析比较中药中汞(Hg)含量测定的电感耦合等离子体质谱(ICP-MS)法、测汞仪(MV)法、原子荧光分光光度(AFS)法和原子吸收分光光度(AAS)法,并采用4种方法测定卷柏总黄酮片及其原料和药材中的汞含量。方法: 建立ICP-MS、MV、AFS和AAS测定汞的方法;采用微波消解法处理样品,分别采用ICP-MS、AFS和AAS方法测定卷柏总黄酮片及其原料和药材中汞的含量;直接进样法用MV测定样品中汞的含量,并对结果进行分析。结果: 卷柏中均未检出汞;AAS除一批总黄酮中汞小于定量限0.050 0mg·kg-1外,其余均未检出汞;总黄酮中汞含量:批号14092101中0.013 9(AFS)、0.014 6(ICP-MS)、0.012 1(MV)mg·kg-1,批号14092102中0.014 2(AFS)、0.013 1(ICP-MS)、0.015 0(MV) mg·kg-1,批号14092103中0.015 1(AFS)、0.016 7(ICP-MS)、0.014 1(MV) mg·kg-1,批号14040101中0.008 7(AFS)、0.008 4(ICP-MS)、0.007 8(MV)mg·kg-1;片剂中汞含量:批号15082801中0.003 5(AFS)、0.003 3(ICP-MS)、0.002 4(MV) mg·kg-1,批号15082802中0.002 3(AFS)、0.002 2(ICP-MS)、0.002 8(MV) mg·kg-1,批号15082803中0.003 1(AFS)、0.003 3(ICP-MS)、0.003 3(MV) mg·kg-1,4种方法测定结果一致。汞的检测限:ICP-MS为0.000 1 mg·kg-1,MV法为0.000 1 mg·kg-1 ,AFS法为0.000 6 mg·kg-1,AAS法为0.015 0 mg·kg-1。4种汞含量测定方法学考察结果良好,标准曲线r均在0.998 6以上,回收率范围为87.4%~100.3%(RSD≤2.9%)。结论: 4种方法均可适用于中药中汞的限量控制,ICP-MS法灵敏度高,可同时检测;MV法不用消解直接进样,简便、快捷、灵敏度高;AFS法简便易行,灵敏度较高;AAS灵敏度较低。
Objective: To compare the inductively coupled plasma mass spectrometry method (ICP-MS), mercury vapourmeter(MV) method, atomic fluorescence spectrometry(AFS) method and atomic absorption spectrometry(AAS) method or determination of mercury (Hg)in Chinese traditional medicine, and determine samples of Selaginella tamariscina, Selaginellae total flavones and tablets of Selaginellae total flavones by the four methods. Methods: Methods of determining Hg were established by ICP-MS, MV,AFS and AAS. Microwave digestion was adopted to treat Selaginella tamariscina, Selaginellae total flavones and tablets of Selaginellae total flavones, and samples were detected by ICP-MS, AFS and AAS, and MV. The contents of their Hg were measured by ICP-MS, MV, AFS and AAS,and the results were analyzed. Results: No mercury was detected in Selaginella tamariscina. Except for a batch of total flavonoids with mercury less than the quantitative limit of 0.050 0mg·kg-1, no mercury was detected in AAS. Mercury content in total flavonoids was 0.013 9 (AFS), 0.014 6 (ICP-MS) and 0.012 1 (MV) mg·kg-1 in batch 14092101, respectively; 0.014 2 (AFS), 0.013 1 (ICP-MS) and 0.015 0 (MV) mg·kg-1 in batch 14092102, respectively; 0.015 1 (AFS), 0.016 7 (ICP-MS) and 0.014 1 (MV) mg·kg-1 in batch 14092103, respectively; 0.008 7 (AFS), 0.008 4 (ICP-MS) and 0.007 8 (MV) mg·kg-1 in batch 14040101, respectively. Mercury content in tablets was 0.003 5 (AFS), 0.003 3 (ICP-MS) and 0.002 4 (MV) mg·kg-1 in batch 15082801, respectively; 0.002 3 (AFS), 0.002 2 (ICP-MS) and 0.002 8 (MV) mg·kg-1 in batch 15082802, respectively; 0.003 1 (AFS), 0.003 3 (ICP-MS) and 0.003 3 (MV) mg·kg-1 in batch 15082803, respectively. The four methods were consistent in determination of Hg. The detection limits of Hg were 0.000 1 mg·kg-1 (ICP-MS),0.000 1 mg·kg-1 (MV), 0.000 6 mg·kg-1(AFS) and 0.015 0 mg·kg-1(AAS),respectively. The four methods of Hg were validated carefully. The linear ranges of Hg were well(r>0.998 6). The recoveries of standard addition ranged from 87.4% to 100.3% (RSD≤2.9%). Conclusion: The four methods can all effectively detect Hg to achieve the purpose of the limit control. The method of ICP-MS had the highest sensitivity and could detect other elements at the same time; MV did not need digestion pretreatment and the sample was injected directly, with the highest sensitivity; AFS had good accuracy, fast response and higher sensitivity; AAS had lower sensitivity.
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