气相色谱-质谱法测定大气颗粒物中的有机胺类物质

摘要

A method was developed for determination of thirteen amines including seven aliphatic amines, two heterocyclic amines and four aromatic amines in atmospheric particulate matter (PM) by gas chromatography-mass spectrometry (GC-MS). Samples were ultrasonically extracted with ultra-pure water and derivatized with benzenesulfonyl chloride (BSC) under alkaline conditions. The derivatives were extracted with dichloromethane and then detected by GC-MS using DB-5MS chromatographic column. The method detection limit (S/N=3) and quantitation limit (S/N=10) were 0.00008-0.017 μg/mL and 0.00026-0.0565 μg/mL respectively, and the correlation coefficients were 0.9903-0.9996, which indicated that the standard curve had good linear correlation. In addition, the relative standard deviation was less than 30％ and the average recovery was 54.4％-159.7％ except for methylamine and benzylamine at spiked level of 1.0 μg/mL, showing high precision and accuracy. 9 kinds of amines were detected in the PM2.5 samples collected in Guangzhou city by this method, among which dimethylamine and butylamine accounted for 90％ of the total nine amines, which indicated that they were primary amines in PM2.5; while propylamine exhibited the lowest level in PM2.5 with the concentration less than 1.0 ng/m3.%建立了大气颗粒物中有机胺类物质的气相色谱-质谱(GC-MS)分析方法.样品用超纯水超声萃取,然后在碱性条件下,用苯磺酰氯(Benzenesulfonyl chloride,BSC)衍生化,衍生物用二氯甲烷萃取,最后用DB-5MS色谱柱分离测定,实现了13种有机胺(包括7种脂肪胺、2种杂环胺和4种芳香胺)的同时测定.本方法的仪器检出限(S/N=3)和定量限(S/N=10)分别为0.00008～0.017 μg/mL和0.00026～0.0565 μg/mL; 标准曲线线性相关系数为0.9903～0.9996,相关性良好;相对标准偏差(RSD)均小于30％, 除低浓度加标水平的甲胺和苯甲胺,其余样品基质加标平均回收率为54.4％～159.7％,大部分胺具有较高的精密度与准确度.将本方法应用于广州城区PM2.5样品的检测, 共检出有机胺9种,其中甲胺、二甲胺和二丁胺约占9种有机胺总和的90％,是PM2.5中主要胺类物质,而丙胺浓度最低,浓度小于1.0 ng/m3.