目的： 采用电感耦合等离子体质谱（ICP-MS）法对大黄中铜（63Cu）、铬（52Cr）、硒（77Se）、铅（208Pb）、砷（75As）、镉（114Cd）、汞（202Hg）7 种有害元素的含量进行测定,并对上述样品中元素量进行比较分析,对大黄药材中有害元素总量做出初步的风险评估,为大黄药材的科学使用和复方制剂中的添加标准提供科学依据。方法： 样品经超高压微波消解后,用超纯水稀释并定容。测汞试样消解后不采取赶酸处理,直接用超纯水稀释并定容;同法制备空白溶液。通过选择合适的同位素,以锗（Ge）、铟（In）、铋（Bi）为内标溶液消除基体干扰,ICP-MS法用动能歧视碰撞反应池技术（KED 模式）测定铜、铬、硒、铅、砷、镉、汞7种有害元素的含量。结果： 7种元素线性关系良好（r≥0.997）,7种元素高、中、低3 种浓度的进样精密度RSD为2.7%~5.4%,加样回收率为90.3%~100.4%,RSD 为1.8%~5.3%,样品在消解后24 h内各元素稳定性良好。13批大黄药材中1批样品镉超标,1批汞超标;大黄药材镉含量超标4.4%,汞含量超标3.5%,铜、铬、硒、铅、砷均未超标。风险评价结果表明：13种大黄药材中重金属及有害元素整体污染水平较低,7种重金属及有害元素的每周平均暴露量均小于世界卫生组织（WHO）规定的理论值。总体风险处于可接受水平,但不同体质和摄入量人群暴露水平有一定差异,应引起重视。结论： 本方法操作简单、快速,样品消解完全,样品污染风险小,通过测定配制标液,进一步优化内标元素浓度,保证高灵敏度,干扰小,能够有效对大黄药材中7 种痕量元素进行定量分析。以风险评估的结果为依据,科学评估了药用大黄药材中有害元素残留产生的风险。
Objective： To establish an inductively coupled plasma mass spectrometry（ICP-MS）method for determination of seven harmful elements（63Cu,52Cr,77Se,208Pb,75As,114Cd and 202Hg）in Rhei Radix et Rhizoma. By comparing the determination results,and preliminarily evaluating the risk of adding rhubarb medicinal materials, the usage and addition criteria of rhizome of Rheum officinale Baill. and Rheum tanguticum Maxim. ex Balf. in compound preparations were provided. Methods： The samples were diluted and capacitated with ultra-pure water after ultra-high-pressure microwave digestion. Mercury specimens were diluted and volume fixed directly with ultrapure water without taking acid treatment after digestion. The blank solution was prepared in the same way. By selecting suitable isotopes,75Ge,115In and 209Bi as internal standard solutions to eliminate matrix interference, ICP-MS method with KED mode（collision reaction cell technology for kinetic energy discrimination）was used to determine the contents of seven hazardous elements（63Cu,52Cr,77Se,208Pb,75As,114Cd and 202Hg）. Results： The linearity of 7 elements was good（r≥0.997）. The RSDs of the injection precision test of the 7 elements at high, medium and low concentrations were in the range of 2.7%-5.4%,the average recoveries were in the range of 90.3%-100.4% with RSDs of 1.8%-5.3%,and the digested solution was stable in 24 h. 13 batches of Rheum officinale Baill. in 1 batch of samples exceeded 4.4% of the standard for cadmium,1 batch of samples exceeded 3.5% of the standard for mercury,while the other 5 elements（63Cu,52Cr,77Se,208Pb,75As）conformed to the standards. The results of risk assessment showed that the overall pollution level of heavy metals and harmful element in 13 batches of Rheum officinale Baill. was low,the average weekly intake of seven heavy metals and harmful elements in rhubarb was less than theoretical value specified by the World Health Organization（WHO）. The overall risk was at an acceptable level,but there were some differences in exposure levels among people with different body types and intakes,which should be taken into account. Conclusion： This method is easy operated and rapid with completely sample digestion and low risk of contamination. The quantitative analysis of seven trace elements in rhubarb herbs can be effectively performed by determining the prepared standard solution and further optimizing the concentration of internal standard elements to ensure high sensitivity and low interference. Based on the results of the risk assessment,the risks arising from the residues of harmful elements in medicinal rhubarb herbs were scientifically evaluated.
[1] 中华人民共和国药典 2015 年版.一部华人民共和国药典 2015 年版.一部[S].2015:23
ChP 2015.Vol ⅠhP 2015.Vol Ⅰ[S].2015:23
[2] 肖雪峰, 黄海波, 郁建生, 等.药用植物大黄的研究现状[J].南方农业, 2018, 12(14):129
XIAO XF, HUANG HB, YU JS, et al.Research status of medicinal plant rhubarb[J].South China Agric, 2018, 12(14):129
[3] 韩小丽, 张小波, 郭兰萍, 等.中药材重金属污染现状的统计分析[J].中国中药杂志, 2008, 33(18):2041
HAN XL, ZHANG XB, GUO LP, et al.Statistical analysis of residues of heavy metals in Chinese crude drugs[J].China J Chin Mater Med, 2008, 33(18):2041
[4] 赵连华, 杨银慧, 胡一晨, 等.我国中药材中重金属污染现状分析及对策研究[J].中草药, 2014, 45(9):1199
ZHAO LH, YANG YH, HU YC, et al.Current situation analysis and countermeasures on contamination of heavy metal in traditional Chinese medicinal materials in China[J].Chin Tradit Herb Drugs, 2014, 45(9):1199
[5] 中华人民共和国药典 2015 年版.四部华人民共和国药典 2015 年版.四部[S].2015:43
ChP 2015.Vol ⅣhP 2015.Vol Ⅳ[S].2015:43
[6] 李耀磊, 张志成, 金红宇, 等.ICP-MS 法测定复方苦参注射液中铜、砷、镉、汞、铅元素的残留量[J].药物分析杂志, 2018, 38(10):254
LI YL, ZHANG ZC, JIN HY, et al.Determination of Cu, As, Cd, Hg, Pb in compound kushen injection by ICP-MS[J].Chin J Pharm Anal, 2018, 38(10):254
[7] 伍国怡. 微波消解ICP-MS 法测定复方丹参片中5 种金属元素含量[J].中国药师, 2016, 19(7):1405
WU GY.Determination of five heavy metals in fufang danshen tablets by inductively coupled plasma mass spectrometry with microwave digestion[J].China Pharm, 2016, 19(7):1405
[8] 张彦辉, 张良圣, 常阳, 等.增压-微波消解电感耦合等离子体质谱法测定含难溶矿物岩石样品中的微量元素[J].铀矿地质, 2018, 34(2):106
ZHANG YH, ZHANG LS, CHANG Y, et al.Determining trace elements in rock samples containing refractory mineralsby pressurize-microwave inductively coupled plasma mass spectrometry[J].Uranium Geol, 2018, 34(2):106
[9] 耿梦晗. 电感耦合等离子体质谱(ICP-MS)在饮用水金属元素分析中的应用研究[D].北京:中国人民解放军军事医学科学院, 2016
GENG MH.A Study into the Application of the ICP-MS with Repect to the Detection of Metallic Elements within Drinking Water[D].Beijing:Academy of Military Medical Sciences, 2016
[10] 谭惠仁. ICP-AES、ICP-MS、AFS、IC 分析技术在茶叶中微量元素的分析研究[D].广州:中山大学, 2013
TAN HR.The Determination of the Trace Elements in Tea Leaves by ICP-AES, ICP-MS, AFS, IC[D].Guangzhou:Sun Yat-sen University, 2013
[11] 王萌萌. ICP-MS 碰撞反应池的研究及人体血清微量元素检测分析方法建立[D].天津:天津大学, 2014
WANG MM.The Research on Collision Reaction Cell and the Establishment of Analysis Method for Detecting Trace Elements in Human Serum[D].Tianjin:TianJin University, 2014
[12] 章颖慧, 王秀英, 杨明, 等.中药有害残留物限量制定原则及其影响因素[J].药物分析杂志, 2015, 35(3):558
ZHANG YH, WANG XY, YANG M, et al.Study on the principle of limit setting for harmful residues in traditional Chinese medicines and the influencing factors[J].Chin J Pharm Anal, 2015, 35(3):558
[13] 左甜甜, 李耀磊, 陈沛, 等.西洋参、山楂、枸杞子中重金属及有害元素残留量测定及初步风险评估[J].药物分析杂志, 2016, 36(11):2016
ZUO TT, LI YL, CHEN P, et al.Determination and preliminary risk assessment of heavy metals and harmful elements in American ginseng, the fruit of Chinese wolfberry and hawthorn[J].Chin J Pharm Anal, 2016, 36(11):2016
[14] 左甜甜, 李耀磊, 金红宇, 等.ICP-MS 法测定18 种动物药中重金属及有害元素的残留量及初步风险分析[J].药物分析杂志, 2017, 37(2):237
ZUO TT, LI YL, JIN HY, et al.Determination of residues of heavy metals and harmful elements in 18 types of animal medicines by ICP-MS and preliminary risk analysis[J].Chin J Pharm Anal, 2017, 37(2):237
[15] 伍彩红, 李倩, 舒眉, 等.广东肉桂中5 种元素的含量测定及分析[J].药物分析杂志, 2018, 38(9):1558
WU CH, LI Q, SHU M, et al.Determination and analysis of five elements in cinnamomi cortex from Guangxi and Guangdong[J].Chin J Pharm Anal, 2018, 38(9):1558
[16] 邱婧, 王湘波, 李瑞莲, 等.ICP-MS 法测定湖南特色中成药中的重金属及有害元素及相关风险评价[J].中南药学, 2019, 17(11):1909
QIU J, WANG XB, LI RL, et al.Risk assessment and determination of heavy metals and harmful elements in Chinese patent medicine from Hunan province[J].Central South Pharm, 2019, 17(11):1909
[17] 童仁平, 樊辰悦, 潘颖.市售中药材类保健食品中铅、总砷、总汞、铬检测及暴露评估初探[J].上海预防医学, 2019, 31(6):448
TONG RP, FAN CY, PAN Y.Detection and exposure assessment of lead, total arsenic, total mercury and chromium residues in Chinese medicine health foods in Shanghai[J].Shanghai J Prev Med, 2019, 31(6):448
[18] 王向未, 仇厚援, 张志恒, 等.食品中膳食暴露评估模型研究进展[J].浙江农业学报, 2012, 24(4):733
WANG XW, QIU HY, ZHANG ZH, et al.Diet exposure assessment methods in food[J].Acta Agric Zhejiang, 2012, 24(4):733
[19] 胡卉, 邵祥龙, 任亚萍, 等.上海市浦东新区中小学生膳食铅暴露水平[J].中国学校卫生, 2020, 41(3):341
HU H, SHAO XL, REN YP, et al.Dietary exposure of lead in primary, middle and high school students in Pudong new area of Shanghai[J].Chin J School Health, 2020, 41(3):341
[20] 李海蓉, 郭亚南, 杨林生.长期饮用砖茶人群铅、硒、砷及汞暴露水平[J].卫生研究, 2017, 46(5):733
LI HR, GUO YN, YANG LS.Exposure levels of lead, selenium, arsenic and mercury in brick-teas from main producing areas in China[J].J Hyg Res, 2017, 46(5):733
[21] 李莹, 胡玉英.虎杖药材中5 种重金属及有害元素含量测定及风险探讨[J].中国药业, 2020, 29(21):49
LI Y, HU YY.Content determination and health risk of five heavy metals and harmful element in Polygonum cuspidatum[J].China Pharm, 2020, 29(21):49
[22] 闻剑, 杨晓东, 尼珍, 等.西藏林芝地区野生食用菌重金属污染状况调查及其暴露评估[J].中国热带医学, 2018, 18(9):881
WEN J, YANG XD, NI Z, et al.Survey of heavy metal pollution and potential risks to human health of wild edible mushrooms in Linzhi Prefecture of Tibet[J].China Trop Med, 2018, 18(9):881
