单壁碳纳米管净化-气相色谱-串联质谱法测定火锅底料中两种邻苯二甲酸酯含量及其风险暴露评估

Determination of 2 kinds of phthalic acid esters in hotpot seasoning by single-walled carbon nanotubes purification-gas chromatography-tandem mass spectrometry and its risk exposure assessment

目的建立单壁碳纳米管净化(single-walled carbon nanotubes,SWCNTs)结合气相色谱-串联三重四极杆质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)检测火锅底料中邻苯二甲酸酯(phthalic acid esters,PAEs)的方法。方法样品经乙腈提取、SWCNT净化,毛细管色谱柱分离后采用GC-MS/MS分析。结果2种PAEs在0.02~1.00μg/mL范围内呈良好线性关系,相关系数均大于0.997,检出限和定量限分别为0.1 mg/kg和0.3 mg/kg,低、中、高3个浓度水平的加标回收率为96.3%~101.9%,精密度为1.0%~3.7%。将所建立方法应用于450批次实际样品检测,发现邻苯二甲酸二丁酯(dibutyl phthalate,DBP)检出率为25.1%,超过0.3mg/kg限量要求样本占比为25.1%;邻苯二甲酸二(2-乙基己基)酯[bis(2-ethylhexyl)phthalate,DEHP]检出率为24.4%,超过1.5 mg/kg限量要求的样本占比为2.0%。用基于蒙特卡洛(Monte Carlo)统计模型的水晶球(Crystal Ball)软件对检测数据进行模拟计算,评估DBP和DEHP的日均暴露量和风险指数,评估发现火锅底料中的DBP、DEHP不存在食品安全暴露风险。结论新建立方法极大地提高净化效果、减少系统污染的可能,在满足检测需求的同时,提升了方法的精密度和准确度。

Objective To establish a single walled carbon nanotube purification(SWCNT)combined with gas chromatography-tandem mass spectrometry(GC-MS/MS)for the detection of phthalates(PAEs)in hot pot base.Method Samples were extracted with acetonitrile,purified with SWCNT,separated by capillary chromatography column,and analyzed by GC-MS/MS.Results The results showed a good linear relationship between the two PAEs in the range of 0.02–1.00μg/mL,with correlation coefficients greater than 0.997.The detection limit and quantification limit were 0.1 mg/kg(S/N=3)and 0.3 mg/kg(S/N=10),respectively.The spiked recovery rates at low,medium,and high concentration levels were 96.3%–101.9%,and the precision was 1.0%–3.7%.The established method was applied to the detection of 450 batches of actual samples,and it was found that the detection rate of dibutyl phthalate(DBP)was 25.1%,with a proportion of 25.1%exceeding the limit of 0.3 mg/kg;the detection rate of bis(2-ethylhexyl)phthalate(DEHP)was 24.4%,and the proportion exceeding the limit of 1.5 mg/kg was 2.0%.Using Crystal Ball software based on Monte Carlo statistical models,the detection data was simulated and calculated to evaluate the daily average exposure and risk index of DBP and DEHP.It was found that there was no food safety exposure risk for DBP and DEHP in the hotpot base.Conclusion The newly established method greatly improves the purification effect and reduces the possibility of system pollution.While meeting the detection requirements,it also enhances the precision and accuracy of the method.