BCR连续提取法联合ICP-MS分析藏药白脉软膏及其矿物原料药中铅、镉、砷、汞、铜元素提取形态

目的：BCR连续提取白脉软膏及其矿物原料药（阳起石、碱花）中的铅、镉、砷、汞、铜元素。按照提取的难易程度划分为不同的提取形态，采用ICP-MS法对不同提取形态的各种元素进行测定，以此对样品中的不同提取形态各元素的含量和分布进行全方位分析。方法：白脉软膏及其矿物原料药（碱花、阳起石）样品经BCR连续提取法处理后，得到残渣态、水溶态、弱酸态、可还原态、可氧化态、总态等供试品溶液，以ICP-MS分别测定铅、镉、砷、汞、铜。结果：按检测样品统计，白脉软膏中铅、镉、砷、汞、铜元素多以残渣态、水溶态存在；阳起石中多以可还原态、残渣态存在；碱花中多以可还原态、可氧化态、残渣态存在。按元素提取形态统计，铅在样品中主要以残渣态、可还原态、可氧化态存在；镉主要以残渣态存在；砷主要以残渣态、弱酸态、可还原态存在；汞主要以可还原态、可氧化态、残渣态存在；铜主要以残渣态、弱酸态、可还原态存在。水溶态和弱酸态在阳起石的5种元素总和中占5.6%，碱花为19.94%，白脉软膏为15.12%。结论：在白脉软膏、阳起石和碱花中，5种元素（铅、镉、砷、汞、铜）在5种元素提取形态（水溶态、弱酸态、可还原态、可氧化态、残渣态）中均有检出，且含量具有比较明显的差异。单从检测数据角度分析，推测样品的安全性符合要求。

Objective:Pb, Cd, As, Hg and Cu in Baimai ointment and its mineral materials (actinolite and trona) were extracted by BCR sequential extraction procedure. According to the difficulty of the extraction, the different extracted forms were divided and determined by ICP-MS. In this way, the content and distribution of Pb, Cd, As, Hg and Cu in different extracted forms were analyzed comprehensively. Methods:After processed by BCR sequential extraction, the samples were divided into residual form, water-soluble form, weak acidulous form, reducible form, oxidable form and total form, then the contents of Pb, Cd, As, Hg and Cu were detected by ICP-MS. Results:According to the statistics of test samples, Pb, Cd, As, Hg and Cu in Baimai ointment were mainly in the forms of residual and water-soluble. Elements in actinolite were mainly in the forms of reducible and residual. And those in trona were mainly in the forms of reducible, oxidable and residual. According to the statistics of elemental extracted forms, Pb was mainly in forms of residual, reducible and oxidable, Cd was mainly in the form of residual, As was in forms of residual, weak acidulous and oxidable, Hg was mainly in forms of reducible, oxidable and residual, and Cu was mainly in forms of residual, weak acidulous and reducible. The water-soluble and weak acidulous forms accounted for 5.6% of the total amount of actinolite, 19.94% of trona, and 15.12% of Baimai ointment. Conclusion:Five elements (Pb, Cd, As, Hg and Cu) were detected in the extraction forms (residual form, water-soluble form, weak acidulous form, reducible form, oxidable form) of Baimai ointment, actinolite and trona, and their contents were obviously different. From the perspective of test data, it is speculated that the safety of samples meets the requirements.

[1] DAS AK, CHAKRABORTY R, CERVERA ML, et al. Metal speciation in biological fluids:a review[J]. Microchim Acta, 1996, 122(3-4):209
[2] 李冰, 杨红霞. 电感耦合等离子体质谱原理和应用[M]. 北京:地质出版社, 2005 LI B, YANG HX. The Principle and Application of ICP-MS[M]. Beijing:Geological Publishing House, 2005
[3] 祖文川, 汪雨, 李冰宁, 等. ICP-MS相关联用技术在食品元素形态分析中的应用及进展[J]. 质谱学报, 2013, 34(4):247 ZU WC, WANG Y, LI BN, et al. The application and development of elemental speciation analysis in foods by ICP-MS related hyphenated technique[J]. J Chin Mass Spectrom Soc, 2013, 34(4):247
[4] 周谙非. 离子色谱-电感耦合等离子体质谱联用测定婴幼儿配方乳粉和米粉中的碘[J]. 粮油食品科技, 2011, 19(1):43 ZHOU AF. Determination of iodine in infant formula milk powder and rice flour[J]. Sci Technol Cereals Oils Foods, 2011, 19(1):43
[5] 高尔乐, 何滨, 江桂斌, 等. 利用碱消解-HPLC-ICP-MS系统测定生物样品中的甲基汞与乙基汞[J]. 环境化学, 2009, 28(2):310 GAO EL, HE B, JIANG GB, et al. Determination of methylmercury and ethylmercury in biological samples using alkaline digestion-HPLC-ICP-MS[J]. Environ Chem, 2009, 28(2):310
[6] 刘丽萍, 吕超, 谭玲, 等. 电感耦合等离子体质谱法测定乳制品中碘含量的方法研究[J]. 质谱学报, 2010, 31(3):138 LIU LP, LÜ C, TAN L, et al. Determination of iodine in dairy products by ICP-MS[J]. J Chin Mass Spectrom Soc, 2010, 31(3):138
[7] 李卫华, 刘玉海. 阴/阳离子交换色谱-电感耦合等离子体质谱法分析鱼和贝类海产品砷的形态[J]. 分析化学, 2011, 39(12):1912 LI WH, LIU YH. Analysis of arsenic speciation in sea fish and shellfish by anion/cation exchange high performance chromatography coupled with inductively coupled plasma-mass spectrometry[J]. Chin J Anal Chem, 2011, 39(12):1912
[8] 中华人民共和国药典2015年版. 四部.[S]. 2015:43(通则<0412>) ChP 2015. Vol Ⅳ[S]. 2015:43(General Rule<0412>)
[9] KARTAL S, AYDIN Z, TOKALIOGLU S, et al. Fractionation of metals in street sediment samples by using the BCR sequential extraction procedure and multivariate statistical elucidation of the data[J]. J Hazard Mater, 2006,132(1):80
[10] 张朝阳, 彭平安, 宋建中, 等. 改进BCR法分析国家土壤标准物质中重金属化学形态[J]. 生态环境学报, 2012, 21(11):1881 ZHANG CY, PENG PA, SONG JZ, et al. Utilization of modified BCR procedure for the chemical speciation of heavy metals in Chinese soil reference material[J]. Ecol Environ, 2012, 21(11):1881
[11] RAURET G, LPEZ-SNCHEZ JF, SAHUQUILLO A, et al. Improvement of the BCR three-step sequential extraction procedure prior to the certification of new sediment and soil reference materials[J]. J Environ Monit, 1999, 1(1):57
[12] 刘丹丹, 刘菲, 缪德仁. 土壤重金属连续提取方法的优化[J]. 现代地质, 2015, 29(2):390 LIU DD, LIU F, MIAO DR. Optimization of soil heavy metal sequential extraction procedures[J]. Geoscience, 2015, 29(2):390
[13] 吴俊斌. 改进BCR提取协同ICP-MS法对大宝山横石河重金属及其形态的分析[D]. 广州:华南理工大学, 2015:5 WU JB. Analysis of heavy metals and their morphology in hengshihe river of dabaoshan by improved BCR extraction and synergistic ICP-MS[D]. Guangzhou:South China University of Technology, 2015:5