高效液相色谱-电感耦合等离子体质谱法检测17种大宗常用中草药中砷元素形态
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摘要
中草药中重金属与有害元素形态分析目前尚处于起步阶段。该研究首先采用电感耦合等离子体质谱(ICP-MS)法检测了17种大宗常用中草药(16种植物药、1种药用真菌)共103个批次中砷(As)总量;进而基于HPLC-ICP-MS建立了中草药中6种As形态的同时检测方法,选择AS7阴离子交换柱,系统分析了17种中草药中的As形态。结果表明微波消解法对药材进行前处理并用ICP-MS检测As总量的方法稳定可靠; As形态分析方面,采用高温超声提取法,6种As形态线性关系良好,相关系数R2>0. 999 9,6种As形态LOQ分别为:砷甜菜碱(As B) 0. 20μg·L~(-1),亚砷酸[As(Ⅲ)]0. 10μg·L~(-1),二甲基砷(DMA) 0. 15μg·L~(-1),砷胆碱(As C) 0. 10μg·L~(-1),一甲基砷(MMA) 0. 25μg·L~(-1),砷酸[As(Ⅴ)]0. 10μg·L~(-1)。加标回收率为84. 24%～121. 5%,相对标准偏差为2. 7%～11%。103批药材中,仅有1批样品As总量超出药典限量标准; 103批药材中As(Ⅲ)和As(Ⅴ)检出率高,其中多数以As(Ⅴ)为主要检出形态,无机As占比达到80. 90%～98. 73%;部分样品检出DMA,MMA和As B,在所有批次中As C均未检出。该研究建立了适合于中草药中As形态的分析方法,为中草药中As形态残留提供了基础数据,可为其风险评估和质量标准的制修订提供重要参考。
The element speciation analysis for heavy metals in herbal medicines is still in the beginning stage. In this study,the total amount of arsenic( As) in 103 batches of 17 commonly used Chinese medicines( including 16 plant medicines and 1 medicinal fungus) was detected by inductively coupled plasma mass spectrometry( ICP-MS). Furthermore,based on HPLC-ICP-MS,the simultaneous detection methods of six As speciation kinds in traditional Chinese medicines were established. An AS7 anion exchange column was selected and the As forms in 17 traditional Chinese medicines was systematically analyzed. The results showed that the method of pretreatment of medicinal materials by microwave digestion and the detection of total amount of As by ICP-MS was stable and reliable. As for the speciation analysis of As,the high-speed ultrasonic extraction method was adopted,and it showed that the linear relationship of the six As speciation was satisfied with the correlation coefficient R2>0. 999 9. The LOQ of six kinds of As speciation were 0. 20,0. 10,0. 15,0. 10,0. 25,0. 10 μg·L~(-1) for arsenic betaine( As B),arsenious acid [As( Ⅲ) ],dimethyl arsenic( DMA),arsenic choline( As C),monomethyl arsenic( MMA),arsenic acid[As( Ⅴ) ],respectively. The recoveries were between 84. 24% and 121. 5%,and the relative standard deviations were 2. 7% to 11%. Among the 103 batches of medicinal materials,only one batch of sample As exceeded the Chinese Pharmacopoeia limit standard; As( Ⅲ) and As( Ⅴ) had high detection rate in 103 batches of Chinese herbal medicines,within which As( Ⅴ) was the main detected form,and inorganic As accounted for the ratio reached 80. 90%-98. 73%; some samples detected DMA,MMA and As B,As C was not detected in any batch. This study established an analytical method suitable for the speciation of As in Chinese herbal medicines,and provided basic data for As residual residue in Chinese herbal medicines,which can provide important reference for the risk assessment and quality standards.
The element speciation analysis for heavy metals in herbal medicines is still in the beginning stage. In this study,the total amount of arsenic( As) in 103 batches of 17 commonly used Chinese medicines( including 16 plant medicines and 1 medicinal fungus) was detected by inductively coupled plasma mass spectrometry( ICP-MS). Furthermore,based on HPLC-ICP-MS,the simultaneous detection methods of six As speciation kinds in traditional Chinese medicines were established. An AS7 anion exchange column was selected and the As forms in 17 traditional Chinese medicines was systematically analyzed. The results showed that the method of pretreatment of medicinal materials by microwave digestion and the detection of total amount of As by ICP-MS was stable and reliable. As for the speciation analysis of As,the high-speed ultrasonic extraction method was adopted,and it showed that the linear relationship of the six As speciation was satisfied with the correlation coefficient R2>0. 999 9. The LOQ of six kinds of As speciation were 0. 20,0. 10,0. 15,0. 10,0. 25,0. 10 μg·L~(-1) for arsenic betaine( As B),arsenious acid [As( Ⅲ) ],dimethyl arsenic( DMA),arsenic choline( As C),monomethyl arsenic( MMA),arsenic acid[As( Ⅴ) ],respectively. The recoveries were between 84. 24% and 121. 5%,and the relative standard deviations were 2. 7% to 11%. Among the 103 batches of medicinal materials,only one batch of sample As exceeded the Chinese Pharmacopoeia limit standard; As( Ⅲ) and As( Ⅴ) had high detection rate in 103 batches of Chinese herbal medicines,within which As( Ⅴ) was the main detected form,and inorganic As accounted for the ratio reached 80. 90%-98. 73%; some samples detected DMA,MMA and As B,As C was not detected in any batch. This study established an analytical method suitable for the speciation of As in Chinese herbal medicines,and provided basic data for As residual residue in Chinese herbal medicines,which can provide important reference for the risk assessment and quality standards.
引文
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[19]张海珠,周萍,史志婷,等.松属植物重金属的含量测定[J].中国实验方剂学杂志,2013,19(24):63.
[20]刘威,王振中,胡军华,等.ICP-MS对牡丹皮中24种微量元素的形态及其溶出特性分析[J].中国实验方剂学杂志,2017,23(3):39.
[21]李耀磊,金红宇,项新华,等.药品中重金属及有害元素残留检测能力验证结果评价模式探讨[J].中国中药杂志,2019,44(8):1724.
[2]赵英福,袁福龙.高效液相色谱分离中药中砷条件的优化[J].医学研究杂志,2006,35(7):87.
[3]袁宇琳,张静,毛腾霄,等.成都市售即食中药预包装产品重金属含量分析及健康风险评估[J].中国实验方剂学杂志,2018,24(24):213.
[4]杨惠芬,梁春穗,董仕林,等.食品中无机砷限量卫生标准的研究[J].中国食品卫生杂志,2003,15(1):27.
[5]骆骄阳,刘好,谷善勇,等.31种动物药中汞、砷元素形态残留分析与限量标准探讨[J].药学学报,2018,53(11):1879.
[6]冯光泉,刘云芝,张文斌,等.三七植物体中重金属残留特征研究[J].中成药,2006,28(12):1796.
[7]陈锐,龚瑞忠,江希流,等.苏州市郊花、果、茶重金属含量调查[J].生态与农村环境学报,1985,1(1):57.
[8] Pell A,Kokkinis G,Malea P,et al. LC-ICP-MS analysis of arsenic compounds in dominant seaweeds from the Thermaikos Gulf(Northern Aegean Sea,Greece)[J]. Chemosphere,2013,93(9):2187.
[9] Chen S,Yuan B,Xu J,et al. Simultaneous separation and determination of six arsenic species in Shiitake(Lentinus edodes)mushrooms:method development and applications[J]. Food Chem,2018,262:134.
[10]丁锐,王瑾,王英华,等.不同产地甘草中微量元素含量的研究[J].药物分析杂志,2010(6):1012.
[11]祖文川,汪雨,刘聪,等.高效液相色谱-原子荧光光谱联用技术分析6种植物源性中药中砷的形态[J].分析试验室,2016,35(1):82.
[12]李邦进.高效液相色谱-电感耦合等离子体质谱检测中药中的五种砷形态[J].福建分析测试,2018,27(3):20.
[13]吕翔,王佳佳,邵霞,等.砷元素形态分析和在中药研究中的应用进展[J].中成药,2017,39(8):1679.
[14]郝春莉,赵丽,庄峙厦.HPLC-ICP/MS联用同时分析中药材中的多种形态砷[J].分析试验室,2011,30(6):90.
[15]田雨,蔡璇,郑锡波,等.高效液相色谱-氢化物发生-原子荧光光谱法分析桂皮中砷形态化合物的检测方法[J].化学工程师,2014,221(2):19.
[16]唐艳梅,黎其万,刘宏程,等.离子交换树脂-原子荧光光谱法测定三七中的4种形态砷[J].中成药,2012,34(3):513.
[17]向明钧,李银保,彭湘君,等.氢化物发生-原子荧光光谱法测定7种中草药中不同形态的水溶性砷[J].光谱实验室,2010,27(2):588.
[18]陈岩,王智勇,杨丽杰,等.中药凤尾草不同部位的砷形态分析[J].中国医院药学杂志,2012,32(12):983.
[19]张海珠,周萍,史志婷,等.松属植物重金属的含量测定[J].中国实验方剂学杂志,2013,19(24):63.
[20]刘威,王振中,胡军华,等.ICP-MS对牡丹皮中24种微量元素的形态及其溶出特性分析[J].中国实验方剂学杂志,2017,23(3):39.
[21]李耀磊,金红宇,项新华,等.药品中重金属及有害元素残留检测能力验证结果评价模式探讨[J].中国中药杂志,2019,44(8):1724.