超低温冷冻除脂-气相色谱串联质谱法检测食用植物油中21种邻苯二甲酸酯

Determination of 21 phthalic acid esters in edible vegetable oils by gas chromatography-tandem mass spectrometry with removing fat through ultra low temperature freezing

建立了超低温冷冻除脂-气相色谱串联质谱(GC-MS/MS)检测食用植物油中21种邻苯二甲酸酯(PAEs)的新方法。样品用乙腈提取,经超低温(-80℃)冷冻10 min除脂,再经减压浓缩,以正己烷复溶,采用GC-MS/MS多反应监测模式进行测定。结果表明,在考察浓度范围(1~1000 ng/m L)内21种PAEs均呈现良好线性,相关系数均大于0.999,检出限为0.10~8.52μg/kg,定量限为0.32~28.40μg/kg,加标回收率为74.31%~116.62%,相对标准偏差为1.21%~17.82%。对市售7类19个油样的抽样检测,显示邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸(2-丁氧基)乙酯(DBEP)、邻苯二甲酸二正庚酯(DHP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)共9种PAEs被检出,其中DMP、DBP、DBEP、DHP和DEHP检出率均大于90%,含量范围为105.57~2156.76μg/kg。该方法操作简便,成本低,可用于食用植物油中PAEs的有效测定。

A new method was developed for the determination of 21 Phthalic Acid Esters（ PAEs） in edible vegetable oils by gas chromatography tandem mass spectrometry（ GC-MS/MS） with removing fat through ultra low temperature freezing. With acetonitrile as extractant,sample was extracted and frozen with ultra low temperature at-80 ℃ for 10 min to remove fat,and then the sample solution was evaporated to near dryness by rotary evaporator and redissolved by n-hexane,and then detected by GC-MS/MS under multiple reaction monitoring modes.All analytes had good linearity with correlation coefficient over 0.999 in the investigated range（ 1 ～ 1000 ng/m L）,the limits of detection（ LOD） were 0.10 ～ 8.52 μg/kg,the limits of quantitation（ LOQ） were 0.32～28.40 μg/kg,the recoveries were 74.31% ～116.62% with the relative standard deviation ranged of 1.21% ～17.82%.Seven categories of 19 kinds of vegetable oil were examined,the results indicated that dimethyl phthalate（ DMP）,diethyl phthalate（ DEP）,diisobutylphthalate（ DIBP）,di-n-butyl phthalate（ DBP）,butyl benzyl phthalate（ BBP）,bis（ 2-butoxyethyl） phthalate（ DBEP）,di-n-heptyl phthalate（ DHP）,bis（ 2-ethylhexyl） phthalate（ DEHP） and di-n-octyl phthalate（ DNOP） total of 9 PAEs were detected,including DMP,DBP,DBEP,DHP and DEHP detection rate of more than90% with the content in the range of 105.57 ～ 2156.76 μg/kg. The method was easy to operate and low cost,which could be used for the effective determination of PAEs in edible vegetable oil.