CAJ | 학술논문

目的建立硅胶/N-丙基乙二胺(PSA)混合固相萃取结合气相色谱-质谱联用测定食用植物油中17种邻苯二甲酸酯类化合物(PAE)的方法,并对杭州超市采集的25份塑料桶装食用油的PAEs含量进行评估.方法样品食用植物油加入D4-邻苯二甲酸二(2-乙基)己酯(D4-DEHP)内标应用液,用乙腈提取,旋涡混匀1 min,3050×g离心5min,取上层乙腈相用硅胶/PSA混合固相萃取柱净化,乙腈洗脱,洗脱液在50℃下用氮吹仪吹干,加正己烷定容至1.0 ml,然后用气相色谱质谱测定17种PAE,采用内标法定量,并对方法的检测限、精密度和准确度进行评价.检测了从杭州超市采集的25份塑料桶装食用油的PAE含量.结果采用D4-DEHP内标法,17种PAE在对应的浓度范围内线性较好,相关系数为0.994～1.000,最低检测浓度为0.05 ～0.15 μg/ml,17种PAE加标回收率为78.3％～ 108.9％,RSD为4.3％～12.1％ (n=6),方法检出限为0.1～0.2 mg/kg.杭州市售的25份塑料桶装食用植物油中检出邻苯二甲酸二甲酯(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)、邻苯二甲酸二(2-乙基)己酯(DEHP),检出率分别为12％(3/25)、24％( 6/25)、100％( 25/25)、96％( 24/25)、100％( 25/25),含量范围为＜0.1～1.8 mg/kg,其他12种PAE均未检出；DBP含量范围为＜0.1～1.3 mg/kg,16％ (4/25)超过国家规定的迁移限量值(0.3 mg/kg),DEHP含量范围为0.2～1.8 mg/kg,12％ (3/25)超过国家规定的迁移限量值( 1.5 mg/kg).结论建立的硅胶/PSA混合固相萃取结合气相色谱-质谱联用方法可以满足食用植物油中PAE检测要求；杭州市场采集的25份塑料桶装食用油中检出了DMP、DIBP、DEP、DBP、DEHP等PAE组分.
목적 건립규효/N-병기을이알(PSA)혼합고상췌취결합기상색보-질보련용측정식용식물유중17충린분이갑산지류화합물(PAE)적방법,병대항주초시채집적25빈소료통장식용유적PAEs함량진행평고.방법 양품식용식물유가입D4-린분이갑산이(2-을기)기지(D4-DEHP)내표응용액,용을정제취,선와혼균1 min,3050×g리심5min,취상층을정상용규효/PSA혼합고상췌취주정화,을정세탈,세탈액재50℃하용담취의취간,가정기완정용지1.0 ml,연후용기상색보질보측정17충PAE,채용내표법정량,병대방법적검측한、정밀도화준학도진행평개.검측료종항주초시채집적25빈소료통장식용유적PAE함량.결과 채용D4-DEHP내표법,17충PAE재대응적농도범위내선성교호,상관계수위0.994～1.000,최저검측농도위0.05 ～0.15 μg/ml,17충PAE가표회수솔위78.3％～ 108.9％,RSD위4.3％～12.1％ (n=6),방법검출한위0.1～0.2 mg/kg.항주시수적25빈소료통장식용식물유중검출린분이갑산이갑지(DMP)、린분이갑산이을지(DEP)、린분이갑산이이정지(DIBP)、린분이갑산이정지(DBP)、린분이갑산이(2-을기)기지(DEHP),검출솔분별위12％(3/25)、24％( 6/25)、100％( 25/25)、96％( 24/25)、100％( 25/25),함량범위위＜0.1～1.8 mg/kg,기타12충PAE균미검출；DBP함량범위위＜0.1～1.3 mg/kg,16％ (4/25)초과국가규정적천이한량치(0.3 mg/kg),DEHP함량범위위0.2～1.8 mg/kg,12％ (3/25)초과국가규정적천이한량치( 1.5 mg/kg).결론 건립적규효/PSA혼합고상췌취결합기상색보-질보련용방법가이만족식용식물유중PAE검측요구；항주시장채집적25빈소료통장식용유중검출료DMP、DIBP、DEP、DBP、DEHP등PAE조분.
Objective We aimed to establish a quantified method for the 17 phthalate acid esters (PAE) in edible vegetable oil by gas chromatography-mass spectrometry (GC-MS) with the pretreatment of acetonitrile extraction and silica/N-(n-propyl) ethylenediamine ( silica/PSA ) mixed solid phase extraction column and evaluated the PAE of 25 edible oil samples from supermarkets in Hangzhou city.Methods The internal standard solution (D4-DEHP) was added in edible vegetable oil sample.The analytes were extracted by acetonitrile with 1 min vortex,and centrifuged at 3050 ×g for 5 min.The supematant was then cleaned with silica/PSA column,and eluted with acetonitrile.The elution was dried with N2 flow at 50 ℃ and diluted to 1.0 ml with hexane.Then,17 PAE were tested by GC-MS and quantified with internal standards.The repeatability and sensitivity of the assay were evaluated.PAE were then determined in 25 plastic buckets of edible vegetable oil from supermarkets in Hangzhou city.Results By the quantification of internal standard of D4-DEHP,a good linearity range of related 17 PAE was observed.The correlation coefficient was 0.994 - 1.000 and the standard lowest quantified level was 0.05 -0.15 μg/ml.The spiking recoveries of 17PAE were 78.3％ - 108.9 ％ with the RSD of 4.3％ - 12.1％ (n =6).The method detection limits were0.1 -0.2 mg/kg.In 25 plastic buckets of edible vegetable oil from Hangzhou,DMP,DEP,DIBP,DBP and DEHP were detected at the range of ＜ 0.1 - 1.8 mg/kg and the detection rates were 12％ ( 3/25 ),24％ (6/25),100％ (25/25),96％ (24/25) and 100％ (25/25),respectively.Other 12 PAE was not detected.For DBP with the level of ＜0.1 to 1.3 mg/kg,the results of 16％ (4/25) samples exceeded the regular migrating limit of 0.3 mg/kg.For DEHP of ＜0.2 - 1.8 mg/kg,the data of 12％ (3/25) samples were beyond the regular migrating limit of 1.5 mg/kg.Conclusion The pretreatment by siliea/PSA mixed solid phase extraction column can satisfy the PAE determination requirements in edible vegetable oils.The DMP,DIBP,DEP,DBP and DEHP were dectected from the survey of 25 edible oil samples in Hangzhou city.