海螵蛸中砷形态分析及限量标准研究

Analysis of arsenic speciation in Sepiae Endoconcha and research on its limit standard

海螵蛸是一味常见的海洋动物药,其砷(As)残留水平普遍较高,《中国药典》2010年版一部收录了其总砷限量(不得超过2 mg·kg^-1),2015年版将限量修订为10 mg·kg^-1。然而,目前尚未见海螵蛸中砷形态研究,其安全风险无法准确评估。该研究收集了不同来源的32批海螵蛸样品,采用HPLC-ICP-MS检测其中砷总量和常见的砷形态,包括无机砷(i As)[As(Ⅲ),As(Ⅴ)]和有机砷(MMA,DMA,As C,As B),评估其安全风险并讨论其限量标准。结果显示,海螵蛸中主要的砷形态为As B,其次为DMA,As(Ⅴ)。32批次样品中有9批检测到i As,占比28%,其中As(Ⅲ)最高达103. 3μg·kg^-1,As(Ⅴ)最高达222. 4μg·kg^-1。参考食品中无机砷限量,有18. 75%的样品砷含量超过安全阈值。研究结果表明,海螵蛸中砷总量与形态间并非呈现简单的正相关,总量控制模式存在漏洞,特别是限量放宽后,难以监管因污染等因素造成的i As含量过高的问题。由于i As毒性远高于有机砷,制定海螵蛸中i As形态限量将具有重要的现实意义。

Sepiae Endoconcha is a common marine animal medicine,which generally contains high concentration of arsenic( As).The Chinese Pharmacopoeia( 2010 edition,part I) stipulated that the total As content of Sepiae Endoconcha should not exceed 2 mg·kg^-1,while this limit was revised to 10 mg·kg^-1 in the 2015 edition. So far,there is no research on the speciation of As in Sepiae Endoconcha,which made it hard to accurately evaluate its security risk. In this study,32 batches of Sepiae Endoconcha from different sources were collected. The safety risk assessment was carried out by determining the total As content and As speciation,inorganic As[As( Ⅲ),As( Ⅴ) ]and organic As( MMA,DMA,As C,As B) by HPLC-ICP-MS,and then the limit standard was discussed. The results showed that As B was the main form of As in Sepiae Endoconcha,followed by DMA and As( Ⅴ) . Of the 32 batches of Sepiae Endoconcha,9 batches( accounting for 28%) were detected possessing i As. The maximum concentration of As( Ⅲ) was 103. 3 μg·kg^-1,and the maximum concentration of As( Ⅴ) was 222. 4 μg·kg^-1. According to the limit of i As in food,18. 75% of the samples exceeded the standard. The results indicate that there is no simple positive correlation between total As and As morphology in Sepiae Endoconcha. Besides,there is a risk in the total As limit,especially after the relaxation of the total As limit. The problem of high i As content caused by pollution and other factors is difficult to regulate. Since the toxicity of inorganic As is much higher than that of organic As,it is of great practical significance to establish inorganic As form limits in Sepiae Endoconcha.