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研究生: 陳子瑋
Chen, Tzu-Wei
論文名稱: 使用質譜技術對廢水中全氟及多氟烷基物質進行定量的整合性分析方法
An Integrated Analytical Approach for the Quantification of Per- and Polyfluoroalkyl Substances in Wastewater Samples using Mass Spectrometry
指導教授: 廖寶琦
Liao, Pao-Chi
學位類別: 碩士
Master
系所名稱: 醫學院 - 環境醫學研究所
Department of Environmental and Occupational Health
論文出版年: 2026
畢業學年度: 114
語文別: 英文
論文頁數: 87
中文關鍵詞: 全氟及多氟烷基物質廢水總可氧化前驅物分析液相層析串聯質譜儀
外文關鍵詞: Per- and polyfluoroalkyl substances, Wastewater, Total Oxidizable Precursor Assay, LC-MS/MS
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  • 全氟及多氟烷基物質(PFAS)是一大類具有兩親性結構的有機污染物,憑藉其優良的化學穩定性,常廣泛應用於日常用品、食品包材、半導體製程等領域,隨著人類活動與廢水排放,PFAS於水體環境中不斷遷移與累積,並最終殘留於河川、地下水及水生生物體內,且在數十年來的環境研究中反覆被檢出,長鏈PFAS的健康風險因而逐漸受各國管制及淘汰。液相層析串聯質譜儀(LC-MS/MS)已成為目前定性與定量微量污染物的重要分析工具。然而,現行針對PFAS的標的物分析僅涵蓋數十種常見的化合物,卻難以概括環境中更為複雜的潛在前驅物。為補足此限制,本研究將導入總可氧化前驅物分析(TOPA),旨在將未知PFAS前驅物轉化為可量測之PFAS產物,以推估樣品中無法被定量之PFAS前驅物以及其可能來源貢獻。
    為維持相關產品性能及工業應用,短鏈PFAS替代物陸續被引入使用。美國環境保護署於 2024 年發布的方法1633A,提供了一套用於萃取與定量多達 40 種目標 PFAS 的標準化分析方法,並整合固相萃取、同位素內標校正以及嚴謹的品質控制程序,以達低檢測極限的標準及高度再現性的性能表現。本研究於方法1633A的分析架構下整合TOPA,使分析範圍得以擴展至潛在前驅物所轉化之產物。研究結果顯示,經此分析方法後,共定量出12種PFAS,其中PFBA、PFBS與PFPeA經TOPA處理後濃度呈現顯著上升趨勢,進一步支持前驅物存在之推論與其轉化貢獻。綜上所述,此整合方法有助於揭示科學園區廢水中PFAS之來源與轉化趨勢,並為水體環境監測與風險評估提供更為完整的科學依據。

    Per- and polyfluoroalkyl substances (PFAS) represent a diverse class of amphiphilic organic pollutants characterized by exceptional chemical stability. These substances are extensively utilized in consumer products, food packaging, and semiconductor manufacturing processes. Driven by anthropogenic activities and wastewater discharges, PFAS continuously migrate and accumulate within aquatic environments, persisting in rivers, groundwater, and aquatic organisms. Over decades of environmental surveillance, the repeated detection of long-chain PFAS and their associated health risks have led to increasingly stringent global regulations and phased-out mandates. While liquid chromatography-tandem mass spectrometry (LC-MS/MS) has become an essential tool for the qualitative and quantitative analysis of trace micropollutants, targeted analysis remains restricted to dozens of known compounds, failing to account for the complex spectrum of potential precursors present in the environment.

    To address this limitation, this study incorporates the Total Oxidizable Precursor Assay (TOPA) to convert unknown PFAS precursors into measurable terminal products, thereby estimating the contribution and concentration of otherwise unquantifiable precursors. Concurrently, short-chain PFAS alternatives are being introduced to maintain industrial performance. In 2024, the U.S. Environmental Protection Agency (EPA) released Method 1633, a standardized reference method for the sample preparation and quantification of 40 target PFAS. This method integrates solid-phase extraction (SPE), isotope dilution calibration, and rigorous quality control protocols to achieve low detection limits and high reproducibility.

    In this research, the TOPA protocol was integrated into the analytical framework of EPA Method 1633A`, expanding the scope of analysis to include products derived from precursor transformation. The results identified 12 PFAS species through the integrated workflow, with concentrations of PFBA, PFBS and PFPeA exhibiting significant increases following TOPA treatment. These findings strongly support the presence of precursors and elucidate their transformational contributions. In conclusion, this integrated approach facilitates the identification of PFAS sources and transformation trends in wastewater from science parks, providing a comprehensive scientific foundation for environmental monitoring and risk assessment in aquatic ecosystems.

    Abstract I 摘要 III 致謝 IV Abbreviations (1/2) X Abbreviations (2/2) XI Chapter I. Introduction 1 1.1 Per- and polyfluoroalkyl substances (PFAS) 1 1.2 PFAS in Science Park 5 1.3 Wastewater treatment plants (WWTPs) 6 1.4 EPA Method 1633A 8 1.5 Challenge in targeted analysis 10 1.6 Total Oxidizable Precursor Assay (TOPA) 11 1.7 Limitations of TOPA 13 Chapter II. Objectives 15 Chapter III. Study design 16 Chapter IV. Materials and Method 19 4.1 Chemicals and reagents 19 4.2 Sample collection and preservation 20 4.3 Aqueous sample preparation 21 4.4 Instrumental analysis 22 4.5 Quality Assurance and Quality Control 24 4.6 Data Analysis 29 Chapter V. Results and Discussion 35 5.1 Method Validation 35 5.2 Application to Environmental Samples 44 5.3 Background Contamination 50 Chapter VI. Conclusions 52 References 53 Supplementary information 58

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