以自動加壓流體萃取搭配極致液相層析和大氣壓氣相層析/ 串聯質譜術分析食品包材中的全氟及多氟烷基化合物

Abstract

全氟/多氟烷基化合物(PFAS)，具備防油抗水的性質，廣泛使用於工業及民生 用品之中。過去已有研究指出全氟/多氟烷基化合物與肝臟、心血管、生殖、發育 及免疫系統等相關疾病有關連，部分長碳鏈的全氟/多氟烷基化合物已被列於持久 性有機汙染物之中，故越來越多新型替代物被研發並應用於食品包材的塗層；為 了維持與過往相同的效能，需要使用更大量的新型多氟烷基化合物。與食品包材中短碳鏈多氟烷基化合物相關的研究仍有限，故此篇研究的目的是利用極致液相層析串聯式質譜儀及大氣壓氣相層析串聯式質譜儀優化檢測食品包材中 31 種全氟/多氟烷基化合物的方法並配合全自動加壓流體萃取系統進行樣本前處理。 本研究對層析條件和串聯質譜儀的參數進行了優化。在極致液相層析儀中使用甲醇 和 5-mM 醋酸銨水溶液（pH 7.0，通過氫氧化銨調整 pH 值）的流動相搭配使用 Atlantis Premier BEH C18 AX管柱（50 × 2.1 mm， 1.7 μm）針對 26 種 PFAS 進行分析。多氟烷基磷酸酯 (PAP) 使用 Waters ACQUITY UPLC BEH C18 管柱（50 × 2.1 mm， 1.7 μm）搭配甲醇10-mM N-甲基嗎啡啉進行分析。層析管柱溫度均為 55℃，並在 UniSpray 負離子模式下進行游離。氟調聚物醇(FTOHs)在 Phenomenex Zebron ZB-WAX 氣相層析管柱分離（30 m × 0.25 mm，0.25 μm），並以 APGC 正電模式游離。 在樣本前處理步驟中，首先將100平方公分的樣品裁剪成碎片並使用均質機均質化，使用10毫升的甲醇在70℃下透過自動加壓流體萃取系統萃取 5 分鐘，並進行兩個循環。將萃取液濃縮至1毫升，並通過0.22 μm尼龍過濾盤過濾後上機分析。 方法確效部分，多數待測物於微波爆米花袋的基質效應因子為 91–179%，部分化合物超過180%；萃取效率為 61–124%。同日間與異日間之相對標準偏差大部分在20% 以內，而多數待測物的回收率高於 120%。待測物於微波爆米花袋的偵測極限範圍與定量極限範圍分別為 0.02 – 4.06 ng/dm2與0.03 – 4.06 ng/dm2。 已開發的方法可應用於食品包裝樣本檢測全氟/多氟烷基化合物，評估長鏈PFAS及其替代品對健康影響是一個新興議題。本方法有助於進一步評估將新替代品添加到食品包裝法規的適用性。

Per- and polyfluoroalkyl substances (PFAS) are widely used in industrial and consumer products because of their amphoteric properties. Studies have reported their association with adverse health effects on hepatic, cardiovascular, reproductive, developmental, and immune systems. Some long-chain PFAS have been included in the list of Persistent Organic Pollutants (POPs); therefore, many emerging substitutes are applied to food packaging, and higher quantities of short-chain PFAS are needed to obtain similar performance to long-chain compounds. There are limited reports about concentrations of short-chain PFAS in food packaging. The study objective is to develop and validate an analytical method for determining 31 PFAS in food packaging using an energized dispersive guided extraction (EDGE) automated system for extraction, and Waters ultra-performance liquid chromatography (UPLC) or atmospheric pressure gas chromatography (APGC) coupled with a tandem mass spectrometer (MS/MS) for determination. The analysis of 26 PFAS 31 was performed with a combined mobile phase of methanol and 5-mM ammonium acetate(aq) (pH 7.0, adjusted by ammonium hydroxide) in UPLC used an Atlantis Premier BEH C18 AX column (50 × 2.1 mm, 1.7 µm). Polyfluoroalkyl phosphate esters (PAPs) were analyzed by a Waters ACQUITY UPLC BEH C18 column (50 × 2.1 mm, 1.7 µm). Both column temperature was 55°C. The ionization was done at UniSpray negative mode. Perfluorotelomer alcohols (FTOHs) were separated on a Phenomenex Zebron ZB-WAX column (30 m × 0.25 mm, 0.25 µm) at APGC positive mode. In the sample preparation steps, 100 cm2 samples were cut into pieces and homogenized, and were extracted by EDGE extraction system at 70℃ for two cycles with 10 mL of methanol per cycle. The extracts of all samples were concentrated to 1 mL and filtered through a 0.22-µm nylon filter for further instrument analysis. In terms of method validation, the matrix effect factors of the analytes in microwave popcorn bags were 91-179%; those of perfluorotelomer unsaturated acids (FTUCAs) and polyfluoroalkyl phosphate diesters (diPAPs) were higher than 180%. The extraction efficiency of the analytes was 12 to 146%. The intra- and inter-day precision (%RSD) for most analytes were lower than 20%; the recoveries for most analytes were higher than 120%. The limits of detection (LODs) of the analytes were 0.02–4.06 ng/cm2, and the limits of quantification (LOQs) were 0.03–4.06 ng/cm2. The developed methods could be applied to analyze PFAS in food packaging samples for evaluating the health effects of the long-chain PFAS and their alternatives.