31种动物药中汞、砷元素形态残留分析与限量标准探讨

Speciation analysis of trace mercury and arsenic in 31 kinds of animal drugs and discussion about the limit standards

重金属与有害元素的毒性与其形态直接相关。本文建立了基于HPLC-ICP-MS的动物药中汞、砷形态分析方法,在此基础上检测了31种动物药(含2015版《中国药典》项下29个品种)中不同形态汞、砷的残留量。结果发现,不同形态汞、砷的LOQ为0.1～0.65μg·kg^(-1),回收率为86.9%～116.6%, RSD为1.49%～4.23%。31种动物药共87个批次均检测到Hg^(2+),含量为2.39～6567μg·kg^(-1);12种动物药共33个批次检测到Me Hg,含量为2.83～319.7μg·kg^(-1);所有的动物药样品中均未检测到EtHg。31种动物药批次中不同砷形态的检出率分别为:As(Ⅲ):96.77%,As(Ⅴ):100%,一甲基砷(MMA):45.16%,二甲基砷(DMA):90.32%,砷甜菜碱(AsB):93.55%,砷胆碱(AsC):22.58%。根据不同形态毒性强弱, Hg残留高风险的品种为:蕲蛇、金钱白花蛇、乌梢蛇、蜈蚣; As残留高风险的品种为:地龙、蕲蛇、乌梢蛇、九香虫。本研究可为动物药中重金属风险评估与限量标准制修订提供重要参考。

The toxicity of heavy metals and harmful elements is close related to their speciation.In the present study,the methods for mercury and arsenic speciation analysis based on high-performance liquid chromatography conjunction with inductively coupled plasma mass spectrometry（HPLC-ICP-MS） were established and applied to the determination of 31 kinds of animal drugs,29 of which were included in the Chinese Pharmacopeia（2015 edition）.The results showed that the LODs for all the speciation were within 0.1-0.65 μg·kg-1,and the recoveries were within 86.9%-116.6% with the RSD of 1.49%-4.23%.Inorganic mercury（Hg2＋） was detected in all the 87 batches of samples that came from 31 kinds of animal drugs,and the contents were 2.39-6567 μg·kg-1.Methylmercury（MeHg） was detected in 33 batches of samples that came from 12 kinds of animal drugs,and the contents were 2.83-319.7 μg·kg-1.Ethylmercury（EtHg） were detected in none of the samples.The detection rates of As（Ⅲ）,As（Ⅴ）,monomethylarsononous acid（MMA）,dimethylarsinic acid（DMA）,arsenobetaine（AsB） and arsenocholine（AsC） in the 31 batches of animal drugs was 96.77%,100%,45.16%,90.32%,93.55% and 22.58%,respectively.According to the toxic level of different speciation,the animal drugs with high risks of mercury were Agkistrodon,Bungarus Parvus,Zaocys,and Scolopendra;the animal drugs with high risks were Pheretima,Agkistrodon,Zaocys,and Aspongopus.This study can provide important evidence for the risk assessment,setting and revision of the limit standards of heavy metals and harmful elements.