固相萃取法分析水生生物体中17种酞酸酯类环境激素

水生生物样品去壳、搅碎、匀浆;干货样品则首先烘干、研磨和过筛。以丙酮作为提取剂超声波辅助提取3次,提取液经无水硫酸钠脱水后进行氮吹浓缩;浓缩液经处理过的Florisil硅藻土吸附柱净化和乙酸乙酯/己烷(1/5,V/V)洗脱剂洗脱与浓缩后,采用气相色谱-电子轰击电离源/质谱法进行定性分析与内标法定量分析。实验优化与选择了提取剂的种类、吸附剂的种类及其活化条件、洗脱剂的种类等样品前处理过程,并讨论了分析空白值的控制问题。分析方法的线性相关系数均大于0.99987,方法检出限均小于3.67μg/L,平均加标回收率为64.1%~124%,方法的相对标准偏差均小于16.4%。此分析方法成功地应用于3种鱼类(刀鱼、黑鱼、草鱼)、2种贝类(沙螺、牡蛎)、1种甲壳类(明虾)、1种头足类(章鱼)、2种植物(海带、海藻)和2种干货(干海带、丁香鱼干)样品中17种酞酸酯类环境激素含量的同时分析,所分析的样品都检测到邻苯二甲酸二甲酯、邻苯二甲酸二异丁基酯和邻苯二甲酸二丁酯,在大部分样品中还检测出邻苯二甲酸二乙酯和邻苯二甲酸二乙基己基酯,说明此5种酞酸酯已造成了一定程度的水体污染。

Analysis of 17 Phthalates Environmental Incretion in Aquicolous Organisms by Gas Chromatography-Electron Ionization/Mass Spectrometry

The aquicolous organism samples were shelled,stirred and mixed respectively.The dried samples were dried deeper,rubbed and sifted out.The treated sample was extracted by acetone thrice in ultrasonic bath,then mixed the three extracted solutions.Anhydrous Na2SO4 was used to remove water in extract solution and N2 was used to concentrate the solution.The concentrated solution was transferred to Florisil column and the mixture of acetic ester and alkyl(1/5,v/v) was used to elute it.At last,the treated samples were analyzed qualitatively by gas chromatography-electron impact mass spectrometry(GC-EI/MS),and they were quantified by internal standard method.The conditions of pretreatment such as the selection of the extractant,the sorbent,the sorbent activation method and the eluent were optimized.The problem of controlling analysis blank was discussed.The linear correlation coefficient was higher than 0.9999,the limit of detection was lower than 3.7 g/L,the recovery values were in the range of 64.1% to 124% and the relative standard deviation of the method was lower than 16.4%.This method was successfully applied to analyze seventeen kinds of phthalates of environmental incretion simultaneously in three kinds of fish(saury,snakehead,curcian),two kinds of seashell(sand snail,oyster),one shellfish(prawn),one cephalopod(octopus),two kinds of plant(kelp,seaweed) and two dried food(dried kelp,dried whitebait).Dimethyl phthalate,diisobutyl phthalate and dibutyl phthalate were determined in all samples.Diethyl phthalate and Di(2-ethyl hexyl) phthalate were determined in many samples.It showed that these five kinds of phthalates had polluted the water in a certain extent.