乳粉中氯丙醇脂肪酸酯的气相色谱-质谱检测方法的建立及其污染水平分析  

Development of gas chromatography- mass spectrometry for determination of fatty acid esters of chloropropanols in milk powder and the pollution level of infant formula

作　　者：李珊[1] 苗虹[2,3] 崔霞[2,3] 赵云峰[2,3] 吴永宁[1] 

机构地区：[1]武汉轻工大学食品科学与工程学院,430023 [2]卫生部食品安全风险评估重点实验室 [3]国家食品安全风险评估中心理化实验部

出　　处：《中华预防医学杂志》2015年第6期554-559,共6页Chinese Journal of Preventive Medicine

基　　金：国家重点基础研究发展计划（2012CB720804）

摘　　要：目的建立检测乳粉中氯丙醇脂肪酸酯（简称氯丙醇酯）的同位素稀释气相色谱－质谱（GC－MS）法，采用该方法分析婴幼儿乳粉中氯丙醇酯的污染水平及膳食暴露风险。方法于北京各大型超市分别采集婴幼儿乳粉共111份，以未检出氯丙醇酯的乳粉作为空白样品。样品经正己烷超声提取，以甲醇钠-甲醇溶液进行酯键断裂反应，用硅藻土小柱进行固相支持液液萃取净化，采用七氟丁酰基咪唑进行衍生化反应，衍生物经氯化钠溶液萃取后进行GC—MS测定，以氘代氯丙醇酯为内标进行内标法定量。采用空白样品的加标回收率评价方法的准确度，以回收率的相对标准偏差（RSD）代表方法的精密度。以婴幼儿乳粉中氯丙醇酯污染水平和6月龄婴幼儿乳粉消费量进行氯丙醇酯膳食暴露评估，分别以氯丙醇酯污染水平的平均值牙（95％CI）和P97.5反映一般婴幼儿群体和乳粉高消费量婴幼儿的膳食摄入水平。结果3-氯-1，2-丙二醇脂肪酸II（3一MCPD酯）、2-氯-1，3-丙二醇脂肪酸酯（2-MCPD酯）、1，3-二氯-2-丙醇脂肪酸酯（1，3-DCP脂）和2,3-二氯-1-丙醇脂肪酸酯（2，3-DCP酯）标准曲线的相关系数分别为0．9999、0．9998、0．9995、0．9996，检出限分别为0．005、0．005、0．015、0．015mg/kg，定量限分别为0．015、0．015、0．045和0．045mg／kg。空白样品在0．025、0．050和0．100mg／kg水平的加标回收率在80．3％～111．9％之间，RSD均小于11．4％。111份样品中，3-MCPD酯和2-MCPD酯的检出率分别为77．5％（86／11）、11．7％（13／111），含量范围分别为未检出（ND）-0．230和ND～0．039mg／kg，x^-（95％CI）分别为0．020（0．003—0．113）和0．006（0．005—0．025）mg/kg，P97.5分别为0．113mg／kg和0．025mg/kg；未检出1,3-DCP酯和2，3-DCP酯。6月龄婴儿对3-MCPD酯的膳食摄入量的牙（95％CI）和P97.5分别为0．304�Objective To establish a method for determination of fatty acid esters of chloropropanols （chloropropanols esters） in milk powder by isotope dilution-gas chromatography-mass spectrometry （GC-MS）, and to acquire the pollution level of chloropropanols esters in infant formula and evaluate the dietary exposure risk of chloropropanols esters in infant formula for infants. Methods A total of 111 infant formula samples were collected from supermarkets in Beijing, and the infant formula with no chloropropanols esters detected was served as the blank sample. The samples were ultrasonically extracted with hexane, followed by ester-bond cleavage reaction with sodium methylate-methanol and purification by matrix solid- supported liquid- liquid extraction, then being derivatived with hepta,quoro butyrylimidazoi. After extracted by sodium chloride solution, the derivatives were determined by GC-MS. The concentration of chloropropanols esters were quantified using the deuterium chloropropanols esters as the internal standards. The accuracy of the method was assessed by the recoveries of the blank spiked samples, and the relative standard deviations （RSD） of the recoveries represent the precision of the method. The contamination level of chloropropanols esters and the intake amount of the infant formula of the 6-month infant were used to estimate the dietary exposure assessment, and x^- （95% C/） and P975 of the contamination level of chloropropanols esters were used to represent the average dietary exposure and the high-end dietary exposure. Results The satisfied linear correlations in the range of 0.010-0.800 mg/L was acquired for 3-MCPD esters, 2-MCPD esters, 1,3-DCP esters and 2,3-DCP esters with coefficient correlations of 0.999 9, 0.999 8, 0.999 5 and 0.999 6, respectively. The limits of detection （LOD） and the limits of quantitation （LOQ） for 3-MCPD esters, 2-MCPD esters, 1,3-DCP esters and 2,3-DCP esters were 0.005, 0.005, 0.015, 0.015 mg/kg, and 0.015, 0.015, 0.045, 0.045 mg/kg. The average recov

关 键 词：气相色谱-质谱法 婴儿 食品污染 氯丙醇脂肪酸酯 膳食暴露评估 

分 类 号：O657.63[理学—分析化学] TS252.51[理学—化学]