建立一种同时测定海藻中5种砷形态的高效液相色谱-电感耦合等离子体质谱(high performance liquid chromatography-inductively coupled plasma-mass spectrometry,HPLC-ICP-MS)检测方法。采用阴离子交换色谱柱,以25 mmol/L磷酸二氢铵溶液和水作为流动相梯度洗脱分析。对比2种提取方法对海藻中总砷提取率的影响,并对提取剂浓度、提取温度进行优化。结果表明,硝酸溶液浓度为0.3 mol/L,提取温度为100 ℃条件下,海藻的总砷提取率最高;5种砷形态在各自的质量浓度范围内线性关系良好,仪器精密度良好,加标回收率在79.50%~115.73%;将建立的方法对不同海藻进行测定,结果表明,铜藻、羊栖菜中毒性大的无机砷为主要的砷化物,海带、裙带菜、鼠尾藻中主要以无毒性的AsB形式存在。该方法灵敏度高、简单、快速,适用于分析海藻中的5种砷形态,并为其食用安全及标准制定提供参考。
A method was developed for the simultaneous determination of arsenious acid (As3+),dimethylarsenic acid (DMA),monomethylarsenic acid (MMA),arsenic acid (As5+),and arsenobetaine (AsB) in seaweed by HPLC-ICP-MS. Five arsenic species were separated by an anion exchange column (Hamilton PRP-X100) with 25 mmol/L ammonium dihydrogen phosphate and water as a mobile phase for gradient elution. The effects of two extraction methods on the extraction rate of total arsenic in seaweed were compared,and the concentration and temperature of the extractant were optimized. The results showed that when the concentration of nitric acid solution was 0.3 mol/L and the temperature was 100 ℃,the extraction rate of total arsenic in seaweed was the highest. The linear relationship was good within the detection range,the precision of the instrument was good,and the recovery rate of standard addition was 79.50%-115.73%. The established method was also used to measure different seaweeds. The results showed that most toxic inorganic arsenic in Sargassum horueri and Hizikia fusifarme were the main arsenide,Laminaria japonica,Undaria pinnatifida Suringar,and Sargassum thunbergii were mainly in the form of AsB. This method developed here was sensitive,simple and rapid. It was suitable for the analysis of five arsenic species in seaweed,and provided a reference for its edible safety and related standards.
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