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/串聯質譜術分析紡織品和皮革產品中之全氟與多氟烷基化合物

Abstract

全氟/多氟烷基化合物（PFAS）是一大類有機化合物，其共同特徵為碳鏈上的氫原子全部或部分被替換為氟原子，並包含至少一個全氟甲基基團（-CF₃）或全氟亞甲基基團（-CF₂-）的結構單元。在紡織與皮革產業中，PFAS常作為製程中的加工劑與表面處理劑，賦予產品耐久性防潑水功能。絕大部分PFAS在環境中具高度持久性，有些已被證實具有生物累積性且對人類健康造成不利影響；傳統使用的長碳PFAS已逐步被淘汰與管制，產業也隨之轉向使用新型或替代的PFAS。 目前不同類型 PFAS 在多元應用領域的使用趨勢研究仍不明朗，尤其是紡織品等特定領域的使用情形，相關文獻極為有限。因此，本研究選取市售標榜具有防水或防污功能的紡織與皮革產品，涵蓋服飾、居家用品與功能性產品三大類。樣品以全自動加壓流體萃取系統（EDGE）萃取，並以極致液相層析串聯質譜儀（UPLC-MS/MS）與大氣壓氣相層析串聯質譜儀（APGC-MS/MS），檢測31種PFAS。 本研究首度將全自動加壓流體萃取系統應用於紡織與皮革製品中PFAS的前處理，並同時分析涵蓋短鏈、長鏈及新型替代物等共31種的PFAS。相對於傳統超音波輔助萃取（UAE）需較長時間，EDGE系統提供全自動化且簡便快速的萃取流程。本次優化後的方法可於10分鐘內完成單一樣本萃取，可顯著提高複雜樣品前處理效率。 所有樣品裁切為100 cm²，接著剪成小碎片後以均質機處理。透過全自動加壓流體萃取系統，先以10 mL甲醇於70°C下萃取5分鐘，再以相同溫度、時間使用10 mL丙酮進行第二次萃取。合併之萃取液濃縮至1.5 mL，經0.22 μm尼龍濾膜過濾後進行分析。本研究選用兩種布料作為方法驗證的空白基質31種PFAS於兩種基質中的回收率大多介於70–130%，相對標準差低於20%，偵測極限範圍為0.04–0.44 μg/m²，顯示分析之準確性與再現性良好。 本研究使用上述已開發的方法分析於 19 件市售產品，已開發的方法揭示此類消費性產品為暴露多種 PFAS的潛在來源，初步樣本分析的成果可作為未來暴露評估、健康風險分析及政策制定之重要參採。實際樣品分析結果顯示，不同類型的紡織與皮革品中均可檢出多種 PFAS；由檢出PFAS之輪廓，反映出產業逐步由傳統使用之 PFAS（如 PFOA、PFOS）轉向短鏈或替代型化合物。其中以氟調聚合醇類（FTOHs）中的 8:2 FTOH（13.9–794 ng/dm²）與 10:2 FTOH（5.0–301 ng/dm²）以及多氟烷基磷酸酯類（PAPs）中的6:2 PAP ( 15.4-236 ng/dm²) 與8:2 PAP（7.60-299 ng/dm²）最為常見，在所有樣品中皆有檢出濃度分布範圍廣泛，顯示此類型 PFAS可能為當前具防水防污功能之紡織與皮革製品中的主要應用趨勢。短鏈PFAS（PFCAs為C4–C7，PFSAs為C4–C6）檢出頻率高達89–100%，而大多數長鏈PFAS（超過C8）檢出率較低，介於21–58%。其中C8化合物檢出頻率約為80%，但濃度普遍低於10 ng/dm²。其結果反映出業界為符合日益嚴格的法規限制，已逐步採用短鏈與替代型PFAS作為功能性處理劑，但仍可能殘留部分受管制之長鏈化合物，突顯紡織與皮革品作為潛在新興污染來源的可能性，亦反映其在環境中所扮演之多重且複雜角色。

Per- and polyfluoroalkyl substances (PFAS) are a large class of persistent organic compounds characterized by hydrogen atoms on the carbon chains, in which fluorine atoms entirely or partially replace hydrogen atoms, and most PFAS are persistent in the environment. In the textile and leather industries, PFAS are used as processing aids, surface treatment agents, and coatings. These substances enable products to impart functional properties, such as water durability, oil repellency, and stain-resistance, and increase the longevity of fabrics and leather products. However, growing scientific evidence supports that the environmental persistence and bioaccumulation of PFAS, along with their potential adverse effects on human health, are which have prompted regulatory attention and enforcement worldwide. Adopting alternative compounds has become increasingly common with the gradual phasing out of legacy PFAS. However, studies investigating the usage patterns and application trends of these PFAS remain insufficient, especially in specific products like textiles. Therefore, this study selected samples from commercially available textile and leather products marketed as water- or stain-resistant for the analysis, including the three main categories of apparel, household goods, and functional items. The objective of this study was to optimize and validate an analytical method for measuring 31 PFAS with the employment of an automated energized dispersive guided extraction (EDGE) for sample preparation, followed by separation using ultra-performance liquid chromatography (UPLC) or atmospheric pressure gas chromatography (APGC), and determination by tandem mass spectrometry (MS/MS). This study is the first to apply the EDGE extraction system to extract PFAS from textile and leather products, enabling the simultaneous analysis of 31 PFAS compounds, including short-chain, long-chain, and emerging alternatives. Compared to traditional ultrasound-assisted extraction (UAE), which is time-consuming, the EDGE system offers a fully automated, simple, and rapid extraction process. The optimized method developed in this study allows for extracting a single sample within 10 minutes, significantly improving the efficiency of pretreating complex samples. All samples were cut into 100 cm² sections first, then further cut into small pieces with a pair of scissors before grinding and homogenization, followed by extraction using energized dispersive guided extraction (EDGE) with 10 mL of methanol and acetone, respectively, at 70°C under 30–35 psi. After concentration to 1.5 mL, the extract was filtered through a 0.22-μm Nylon membrane filter and was ready for instrumental analysis. This study selected two fabric types as blank matrices for method validation. Recoveries of the 31 PFAS in these matrices mostly ranged from 70% to 130%, with relative standard deviations (%RSD) below 20%, demonstrating good accuracy and precision. The method was also sensitive, with detection limits between 0.05 and 0.43 ng/dm². The developed method was applied to analyze 19 commercial products, and the results revealed the simultaneous use of multiple PFAS. The study results reflect an industry shift from traditional PFAS (PFOA, PFOS) to short-chain and alternative PFAS. Fluorotelomer alcohols (FTOHs), specifically 8:2 FTOH (13.9–794 ng/dm²) and 10:2 FTOH (5.0–301 ng/dm²), and polyfluoroalkyl phosphoric acid diesters (PAPs), including 6:2 PAP (15.4–236 ng/dm²) and 8:2 PAP (7.60–299 ng/dm²), were the most prevalent. However, they were in a wide concentration range and were detectable in each sample. Short-chain PFAS (C4–C7 for PFCAs, C4–C6 for PFSAs) were frequently detected, with positive rates of 89–100%. In contrast, most long-chain PFAS (above C8) showed lower detection rates of 21–58%. An exception was C8 compounds, which had a relatively high detection frequency (~about 80%) but generally low concentrations (<10 ng/dm²). In summary, this study demonstrated that textile and leather products are potential sources of exposure to PFAS and reflect current usage trends of these substances in consumer goods. These findings provide critical data on PFAS content in various textile and leather materials and serve as an essential reference for future exposure assessment, health risk evaluation, and policy development. Furthermore, the study investigated the PFAS pattern across different categories of textile and leather products, aiming to explore potential new sources of contamination and possible environmental transformation pathways.