GC-MS法测定人参中19种邻苯二甲酸酯类塑化剂及初步风险评估

Determination of 19 phthalic acid esters in Panax ginseng using gas chromatography-mass spectrometry and preliminary risk assessment

目的利用GC-MS法对栽培人参中19种邻苯二甲酸酯类(phthalic acid esters,PAEs)塑化剂[邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丙酯、邻苯二甲酸二烯丙酯、邻苯二甲酸二丙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯]残留量进行测定,并对检出的PAEs做初步的风险评估,以期保证人参的质量安全。方法样品经乙腈提取,N-丙基乙二胺(primary secondary amine,PSA)净化剂进行分散固相萃取净化,经HP-5色谱柱(30 m×0.25 mm×0.25μm)分离,以单离子监测模式(single ion monitor,SIM)进行测定。结果19种PAEs在0.01~0.20 mg/L线性关系良好,r均大于0.9939,4种PAEs(邻苯二甲酸二丙酯、邻苯二甲酸二异丙酯、邻苯二甲酸二环己酯、邻苯二甲酸二正辛酯)在0.005、0.01、0.05 mg/kg添加水平下的平均加标回收率为75.3%~90.8%,RSD为1.6%~5.2%,灵敏度、准确度及精密度均符合要求。结论12批人参样品中有7种PAEs检出;其中邻苯二甲酸二(2-乙基)己酯检出频率最高(100%检出),平均残留量为0.07 mg/kg,最高可达0.17 mg/kg;其次为邻苯二甲酸二异丁酯检出频率为67%,平均残留量为0.13mg/kg,最高可达0.24mg/kg;同时对检出邻苯二甲酸二(2-乙基)己酯进行非致癌性和致癌性风险评估,发现邻苯二甲酸二(2-乙基)己酯通过摄入人参途径的非致癌风险和致癌风险均非常低。

Objective The residues of 19 phthalic acid esters(PAEs)[dimethyl phthalate(DMP),diethyl phthalate(DEP),diisopropyl phthalate(DIPrP),diallyl phthalate,dipropyl phthalate(DPrP),diisobutyl phthalate(DIBP),dibutyl phthalate(DBP),bis(2-methoxyethyl)phthalate(DMEP),bis(4-methyl-2-pentyl)phthalate(BMPP),di(2-ethoxyethyl)phthalate(DEEP),diamyl phthalate(DPP),dihexyl phthalate(DHXP),butyl benzyl phthalate(BBP),bis(2-n-butoxyethyl)phthalate(DBEP),dicyclohexyl phthalate(DCHP),di-(2-ethylhexyl)phthalate(DEHP),dipentyl phthalate(DPhP),di-n-octyl phthalate(DnOP)and dinonyl phthalate(DNP)]in Panax ginseng were determined by gas chromatography-mass spectrometry(GC-MS),and the risk assessment of PAEs was conducted to ensure the quality and safety of P.ginseng.Methods The samples were extracted by acetonitrile and purified by dispersed solid phase extraction with PSA,which were separated on an HP-5 column(30 m×0.25 mm×0.25μm)and determined by single ion monitoring(SIM).Results A total of 19 kinds of PAEs had good linearity in the range of 0.01 to 0.20 mg/L,with correlation coefficients greater than 0.9939.The average recoveries of four kinds of PAEs(DPrP,DIPrP,DCHP and DnOP)at 0.005,0.01 and 0.05 mg/kg were between 75.3%and 90.8%,and RSD were between 1.6%and 5.2%.All the sensitivity,accuracy and precision meet the requirements.Conclusion Seven PAEs were detected in 12 batches of P.ginseng samples.The detection frequency of DEHP was 100%,which average residue was 0.07 mg/kg and the highest residue was 0.17 mg/kg,followed by DIBP with a 67%detection frequency which average detection amount was 0.13 mg/kg,and the highest residue was 0.24 mg/kg.At the same time,the non-carcinogenic and carcinogenic risks of DEHP detected were evaluated,and it was found that the non-carcinogenic and carcinogenic risks of DEHP through intake of P.ginseng were very low.