全二维气相色谱-飞行时间质谱法测定消费品中20种邻苯二甲酸酯类塑化剂

Determination of 20 Phthalates in Consumer Products by Two-dimensional Gas Chromatography-Time-of-flight Mass Spectrometry

该文建立了日用消费品中20种邻苯二甲酸酯类塑化剂的全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)筛查与定量检测方法。样品破碎后采用正己烷超声提取,提取液经石墨化炭黑(GCB)和无水硫酸镁(MgSO 4)分散固相萃取净化,GC×GC-TOF MS检测,飞行时间质谱定性,外标法定量。结果显示,20种邻苯二甲酸酯类塑化剂在0.03~30 mg/L质量浓度范围内呈良好线性,相关系数(r^2)大于0.99,方法的检出限为0.09~22.13 mg/kg,定量下限为0.25~63.1 mg/kg,在低、中、高3个加标浓度水平下的回收率为63.2%~120%,相对标准偏差(RSD,n=6)为0.30%~10%。将该方法用于实际样品检测,在1例塑料样品中检出邻苯二甲酸二异壬酯,含量为1.55 mg/kg,在1例橡胶样品中检出邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基)己酯,含量分别为1.48 mg/kg和7.66 mg/kg。该方法准确、高效,前处理操作简单,可同时实现包含5种异构体的20种邻苯二甲酸酯类塑化剂的筛查和确证。

An analytical method was developed for screening and quantitative detection of 20 phthalates(PAEs)in consumer products by two-dimensional gas chromatography-time-of-flight mass spectrometry(GC×GC-TOF MS).Samples were shattered,and followed by ultrasonic extraction with hexane.The extract was purified by dispersive solid-phase extraction(dSPE)with graphitized carbon black(GCB)and magnesium sulfate anhydrous(MgSO4),analyzed by time-of-flight mass spectrometry and quantified by external standard method.Experimental results demonstrated that there were good linear relationships for 20 PAEs in the range of 0.03-30 mg/L with their correlation coefficients(r^2)larger than 0.99.The limits of detection(LODs)and limits of quantitation(LOQs)were in the ranges of 0.09-22.13 mg/kg and 0.25-63.1 mg/kg,respectively.The recoveries at low,medium and high three spiked levels ranged from 63.2%to 120%with relative standard deviations(RSDs,n=6)of 0.30%-10%.This method was practically used in the detection for different samples.Results showed that diisononyl phthalate was found containing 1.55 mg/kg in a plastic sample,and dibutyl phthalate and di(2-ethylhexyl)phthalate were 1.48 mg/kg and 7.66 mg/kg in a rubber sample,respectively.This method could be applied in the determination of 20 phthalates including 5 phthalate isomers in consumer products with accuracy,efficiency and easy pretreatment.