【作者】 刘慧婷；

【导师】 应义斌； 陈笑梅；

【作者基本信息】 浙江大学 ， 生物系统工程， 2011， 硕士

【摘要】 全氟化合物是一类工业化合物,具有广泛存在性、难降解性、生物积累性的特点,对食品安全、人类健康和生存环境造成影响。食品接触材料中的全氟化合物可能会污染与它接触的食品,而食用被污染的食品是持久性污染物暴露于人类的最主要的方式。针对欧盟对于纺织品和皮革中全氟化合物的限定,目前国内企业并没有研究很好的替代品。对食品接触材料及纺织品、皮革中全氟化合物的检测方法进行研究并对结果进行分析具有重要意义。建立基于液相色谱-串联质谱法的纺织品中全氟化合物的检测方法。比较了索氏法、离子配对法、超声波三种方法的提取效率,对提取溶剂和时间进行了选择和优化,最终确定的纺织品最优前处理方法是以甲醇为溶剂,超声波提取40 min。为减小纺织品的基质效应,根据基质加标标准曲线进行定量。本方法的添加回收率为84.6%-111.8%,检出限为0.5μg/m2,多个涂层纺织品被检测超出全氟辛烷磺酸(PFOA)欧盟指定针对纺织品1μg/m2的限定标准。对皮革中全氟化合物的检测方法进行研究。采用快速溶剂萃取仪提取,优化了温度、溶剂、循环次数等实验条件。为减小皮革的基质效应,采用固相微萃取柱进行萃取净化,并根据基质加标标准曲线进行定量。本方法的添加回收率为80.3%～115.9%,检出限为5μg/kg。本方法用于52个皮革实样的检测,36个样品被测出全氟化合物,检出率很高,最高浓度达284.47μg/kg。全氟辛酸和全氟辛烷磺酸,是检出的最主要的全氟化合物。采用超声法提取,高效液相色谱-串联质谱仪检测食品接触材料中的十种全氟化合物。本方法添加回收率为90.6%-112.8%,检出限为0.5μg/m2。收集的100个食品接触材料样品,全氟化合物最高浓度达317.24μg/m2。17%的样品被检测含有PFOA,16%的样品被检测含有全氟辛酸(PFOS)。12个品牌的快餐包装袋中,一半被检出全氟化合物,浓度范围为6.80～142.68μg/m2。4个品牌的微波炉爆米花包装袋均被检出全氟化合物,浓度范围为46.24～196.64μg/m2。采用单因素方差分析方法对全氟羧酸类化合物的相关性进行分析,结果表明,PFHxA、PFNA、PFOA、PFDA、PFUnDA和PFDoDA之间存在正相关性(R2>0.735,P<0.05)。更多还原

【Abstract】 Perfluorinated compounds, as a group of industrial chemicals, which have three features, widespread existence in environment, hard degradation and biological accumulation, have affected human health and environmental safty. PFCs in food-contact materials may contaminate the food they contact. European Union (EU) limited the use of perfluorooctane sulfonate (PFOS) in textile and leather in European markets and there were no potential substitute goods. Therefore, it’s important to establish methods for detecting PFCs in food-contact materials, textile and leather.The method was established to determine ten PFCs in textile goods by HPLC-MS/MS. We compared extraction efficiency of three methods, including soxhlet method, ion pairing method and ultrasonic method, and optimized the extraction solvents and time. Finally the ultrasonic extraction method with methanol as the solvent and 40 min as the extraction time was selected. Matrical standard curve was used to minimize matrix effect. The limit of detection and recovery range of the method were 0.5μg/m2 and 84.6%-111.8%, respectively. For real samples detection, some coated textiles were detected to contain PFOS more than 1μg/m2.The detection method for PFCs in leather was also studied. ASE was used to extract PFCs in leather and three experimental conditions (temperature, solvent and recycle times) were optimized. SPE purification and matrical standard curve were used to minimize matrix effect. The limit of detection and recovery range of the method were 5μg/kg and 80.3%～115.9%, respectively.36 of the total 52 leather samples were detected to contain PFCs, and the highest concentration of PFCs was 284.47μg/kg. PFOA and PFOS were the main PFCs in leather.PFCs in food-contact materials were extracted by ultrasonic and detected by HPLC-MS/MS. The limit of detection and recovery range of the method were 0.5μg/m2 and 90.6%～112.8%, respectively. Among the 100 food-contact samples, the highest concentration of PFCs was 317.24μg/m2.17 samples were detected to contain PFOA, while 16 contain PFOS. Half of the 12 fast food packaging samples were detected to contain PFCs ranged from 6.80～142.68μg/m2. All of the 4 popcorn packaging samples were measured to have PFCs ranged from 46.24～196.64μg/m2. One way analysis of variance (ANOVA) was used to analyze the relationship among PFCs and there were statistically significant positive correlations between two PFCs among PFHxA, PFOA, PFNA, PFDA, PFUnDA and PFDoDA (R2>0.735, P<0.05).更多还原