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    超声提取-气相色谱-质谱法测定塑料快递包装中6种邻苯二甲酸酯类增塑剂的含量

    Determination of 6 Phthalate Esters in Plastic Express Package by Gas Chromatography-Mass Spectrometry with Ultrasonic Extraction

    • 摘要: 鉴于现用标准的前处理方式存在操作复杂、耗时较长及设备昂贵等问题,选用易于实现的超声提取技术,通过考察不同提取条件对质控样中邻苯二甲酸酯(PAEs)类增塑剂提取效果的影响,提出了超声提取-气相色谱-质谱法测定塑料快递包装中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二异壬酯(DINP)和邻苯二甲酸二异癸酯(DIDP)等6种PAEs类增塑剂含量的方法。将塑料包装样品剪成小块,称取0.5 g于玻璃萃取瓶中,加入20 mL二氯甲烷,于25℃超声30 min,上清液经0.45 μm有机滤膜过滤,再加入一定量的邻苯二甲酸二戊酯(内标)溶液,使其质量浓度为5.0 mg·L-1。6种PAEs在DB-5MS毛细管色谱柱上以柱升温程序的方式进行分离,用配有电子轰击离子源的质谱仪以全扫描方式进行检测,内标法定量。结果显示:6种PAEs标准曲线的线性范围为0.10~5.0 mg·L-1(DBP、BBP、DEHP和DNOP)和1.0~50 mg·L-1(DINP和DIDP),检出限(3S/N)为0.03~0.63 mg·kg-1;对空白样品进行加标回收试验,6种PAEs的回收率为92.2%~105%,测定值的相对标准偏差(n=6)为0.76%~3.2%;方法用于10个塑料快递包装样品分析,除两种样品检出DBP和DEHP外,其他样品中均未检出目标物;对比了超声提取法、索氏提取法(GB/T 22048-2015)和微波消解法(SN/T 2249-2009)对质控样和实际样品测定结果的影响,质控样的测定结果均在认定值的不确定度范围内,实际样品中有3个样品检出DBP和DEHP,其余样品中均为未检出目标物,并且这3种前处理方式所得结果接近。

       

      Abstract: In view of the problems of complex operation, long time consuming and expensive equipment in the pretreatment methods adopted by current standards, ultrasonic extraction technology, which was easy to implement, was selected. The effects of different extraction conditions on the extraction effect of phthalate esters (PAEs) in the quality control sample was investigated, and a method for the determination of 6 PAEs, including dibutyl phthalated (DBP), butyl benzyl phthalate (BBP), bis (2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl phthalate (DINP) and di-iso-decyl phthalate (DIDP) in plastic express package by gas chromatography-mass spectrometry with ultrasonic extraction was proposed. The plastic package sample was cut into small pieces, and 0.5 g of an aliquot and 20 mL of methylene chloride were added into a glass extraction bottle, and ultrasonic extraction was performed for 30 min at 25℃. The supernatant was filtered by 0.45 μm organic filter membrane, and a certain amount of dipentyl phthalate (internal standard) solution was added to make its mass concentration to 5.0 mg·L-1. The 6 PAEs were separated on DB-5MS capillary column with column temperature program, detected by mass spectrometer equipped with electron impact ionization and full scanning mode, and quantified by internal standard method. It was shown that the linear ranges of standard curves of 6 PAEs were 0.10-5.0 mg·L-1 (DBP, BBP, DEHP and DNOP) and 1.0-50 mg·L-1 (DINP and DIDP), with detection limits (3S/N) in the range of 0.03-0.63 mg·kg-1. Test for recovery was made on blank sample by addition standard method, giving results of 6 PAEs in the range of 92.2%-105%, and RSDs (n=6) of the determined values were ranged from 0.76% to 3.2%. This method was applied to the analysis of 10 plastic express package samples, DBP and DEHP were detected in two samples, and the targets were not detected in the other samples. The effects of ultrasonic extraction method, Soxhlet extraction method (GB/T 22048-2015) and microwave digestion method (SN/T 2249-2009) on the determined results of the quality control sample and actual samples were compared, and the determined results of the quality control sample were within the uncertainty ranges of the certified values. DBP and DEHP were detected in 3 actual samples, the targets were not detected in the other samples, and the results obtained by the 3 pretreatment methods were similar.

       

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