电感耦合等离子体质谱法半定量快速筛查13种中药材中重金属及毒性元素

Semi-quantitative analysis of heavy metals and toxic elements in 13 traditional Chinese medicines by inductively coupled plasma mass spectrometry

目的:采用电感耦合等离子体质谱法(ICP-MS法)建立具有一定通用性的、无需大量对照物质的重金属及毒性无机元素半定量快速分析方法,用于对于中药中所含未知元素的快速筛查和分析。方法:中药材经微波消解前处理后,采用ICP-MS半定量测定方式,选择扫描全谱范围内所有元素,测定重金属及毒性元素。等离子气流量:15.0 L·min^(-1);蠕动泵:0.20 r·s^(-1);雾化室温度:2℃;辅助气流量:0.8 L·min^(-1);载气流量:0.8 L·min^(-1);射频功率:1 550 W;测量点数:6;扫描次数:100次;重复次数:1次;碰撞模式:He模式;分析模式:半定量。结果:西洋参、甘草、川芎、黄连、紫苏叶、金银花、山楂、枸杞子、胖大海、陈皮、白花蛇舌草、水蛭、海藻中Pb、Cd、As、Hg、Cu的回收率为80%~120%。黄连、川芎、白花蛇舌草中Cd的残留量,海藻中Hg的残留量,白花蛇舌草中Pb的残留量,水蛭中As的残留量超标。多元素测定结果表明,Mn、Fe、Zn在药材中含量均较为丰富,其含量范围分别为4.61~910.80、29.27~1 771.27和2.80~276.25 mg·kg^(-1);Ni、Cr、V在药材中均有一定的含量(含量范围分别0.04~15.30、0~28.22和0.02~11.12 mg·kg^(-1)),其中海藻中这3种元素的含量(含量范围分别为1.47~14.30、10.15~28.22和0.37~11.12 mg·kg^(-1))高于其他药材。结论:本研究建立的半定量分析方法,适用于中药中多种重金属及毒性元素的半定量快速筛查,操作简便,结果准确,效率较高。所建立的方法可以实现对于未知盲样所含未知元素的快速筛查,能够快速确定有害目标元素及浓度范围,为有效应对中药药害事故提供科学依据。

Objective： To establish a universal and semi-quantitative analytical method of heavy metals and toxic inorganic elements in traditional Chinese medicines （ TCMs ） without using a large amount of reference substances by inductively coupled plasma mass spectrometry （ ICP-MS ）, for the rapid screening of unknown elements in TCMs. Methods： After samples were pretreated by microwave digestion, the ICP-MS semiquantitative determination method was adopted. And all elements were measured in a full spectral range mode. The determination conditions were as follows： plasma gas flow： 15.0 L·min-1; peristaltic pump： 0.20 r·s-1; spray chamber temperature： 2℃ ; auxiliary gas flow rate： 0.8 L·min -1; radio frequency power： 1 550 W; measurement points ： 6; scanning times ： 100; repeat times ： 1 ; collision mode ： He mode ; acquisition mode ： semi-quantitative mode. Results： The recovery rates of Pb, Cd, As, Hg and Cu in Panacis Quinquefolii Radix, Glycyrrhizae Radix et Rhizoma, Chuanxiong Rhizoma, Coptidis Rizoma, Perillae Folium, Lonicerae Japonicae Flos, Crataegi Fructus, Lycii Fructus, Sterculiae Lychnophorae Semen, Citri Reticulatae Pericarpium, Hedyotis diffusa, Hirudo and Sargassum, were in the range of 80%-120%. The contents of Cd in Coptidis Rhizoma, Chuanxiong Rhizoma and Oldenlandiae Diffusae Herba exceeded the limits. The Hg contents in Sargassum, the Pb contents in Oldenlandiae Diffusae Herba and the As contents in Hirudo exceeded the limits. Multi-element determination results showed that Mn, Fe and Zn contents in TCMs were abundant with contents range of 4.61-910.80 mg·kg-1, 29.27- 1 771.27 mg·kg-1 and 2.80-276.25 mg·kg-1, respectively. Ni, Cr and V were found in these TCMs with contents range of 0.04-15.30 mg·kg-1, 0-28.22 mg·kg-1 and 0.02-11.12 mg·kg-1, respectively. The contents of Ni, Cr and V in Sargassum were higher than those in other TCMs with contents range of 1.47-14.30 mg·kg-1, 10.15-28.22 mg·kg-1 and 0.37-11.12 mg· kg-1, respectively. Conclusion： The established semi-quantitative analysis method can be applied to the semi-quantitative rapid screening of various heavy metals and toxic elements in TCMs, which is simple, accurate and efficient. The established method can realize rapid screening for unknown elements in samples, and can realize the rapid determination of the target harmful elements and their range of contents in the samples. And the established method can provide scientific basis for detrimental accidents caused by TCM.