新興污染物之廣泛存在，已對環境健康與生態系統完整性構成重大挑戰。雖然水體被視為污染物傳輸的主要途徑，固體環境基質往往作為此類持久性污染物最終匯集的「吸附匯」或「庇護所」。本研究旨在探討持久性新興污染物於固相介質中的宿命、傳輸與累積機制。具體而言，本研究探討於不同環境介質中固體基質對新興污染物宿命、傳輸與累積行為，分別以全氟烷基酸物質 (PFAAs) 於室內灰塵與高有機質土壤改良劑中之累積與傳輸，以及塑膠微粒 (MPs) 於河流流域尺度中作為顆粒污染物的宿命為研究對象。
本研究第一部份(第三章)，針對台灣台南地區多樣化的室內微環境 (實驗室、辦公室、宿舍和教室)，分析了室內灰塵樣本中的 PFAAs 特徵。結果顯示 PFAAs 具有顯著的空間異質性，其中實驗室(中位數濃度 ΣPFAAs: 528.9 μg/kg) 與辦公室(中位數濃度 ΣPFAAs: 304.2 μg/kg) 被鑑定為主要的暴露熱點，其濃度顯著高於宿舍(中位數濃度 ΣPFAAs: 180.1 μg/kg) 與教室(中位數濃度 ΣPFAAs: 105.1 μg/kg)。本研究應用逐步群集分析證實室內灰塵中 PFAAs 的累積並非由 總有機碳「含量」主導，而是由陽離子含量與水分含量透過靜電與界面吸附作用所控制。健康風險評估顯示，透過室內灰塵暴露PFAAs之整體風險尚在可接受範圍 (Hazard Quotient<1)，但在高使用率的環境中，經由灰塵攝入的慢性暴露仍值得關注。
承接第三章的發現，於第四章中，本研究進一步闡明了有機碳「品質」與「含量」 對 PFAAs 吸附的辯證關係。透過批次與管柱實驗比較了兩種高碳含量的土壤改良劑：泥炭土與豬糞堆肥 (CSM)。結果顯示，儘管 CSM 的有機碳含量低於泥炭土，但其對長鏈 PFAAs 展現出顯著較高的吸附親和力與遲滯。本研究證實，有機質的孔隙結構（「窄喉」效應）與特定的官能基組成（含氮基團）是決定PFAAs遲滯的關鍵，而非僅取決於碳總量。
於第五章，本研究透過全年度的監測，解析了鹽水溪流域中塑膠微粒的時空分布。研究發現 MPs 檢出率100%，河川水體平均豐度為235.1 items/L，而作為主要匯的底泥 (平均 20,370 items/kg)，其累積濃度比水體高出 1-2 個數量級。冗餘分析指出農業土地利用是水體污染的主要驅動因子。本研究觀察到明顯的季節性「沖刷與填充」機制：豐水期的水流會動員MPs(沖刷)，而枯水期的低流量則促進較高密度聚合物在底泥中的沉積 (填充)。此外，本研究揭示了關鍵的「豐度-風險脫節」現象。雖然基於豐度的指標(污染負荷指數 PLI）顯示風險較低，但基於毒性的指標 (聚合物風險指數 PRI) 卻揭示了由 PVC 和 PU 等高危害聚合物驅動的高生態風險，凸顯了進行聚合物特異性風險評估的必要性。
綜合上述研究結果，本研究指出 PFAAs 於固體介質中的行為主要受物理化學交互作用（包含靜電力、含水率與有機質品質）所控制，而河川沉積物中微塑膠的分布與累積則主要由流域尺度之水文動力與土地利用型態所驅動。基於此，本研究主張環境管理策略應由傳統之濃度監測，轉向以有機質特性與聚合物毒性為核心的管理模式，以有效降低「永久性化學物質」與塑膠污染於固體環境基質中的長期風險。整體而言，本研究確立固體環境基質（包含室內粉塵、有機質改良土壤與河川沉積物）是持久性污染物滯留、傳輸與風險的「匯」，並強調未來污染物宿命評估與環境管理體系中，納入基質特異性機制之必要性。

The ubiquity of emerging contaminants (ECs) poses a significant challenge to environmental health and ecosystem integrity. While water is considered the primary transport vector, solid matrices often function as the ultimate "sinks" or "shelters" for these persistent contaminants. This study investigates the fate, transport, and accumulation mechanisms of ECs across distinct environmental compartments. Specifically, this study examines perfluoroalkyl acids (PFAAs) in indoor dust and organic-amended soils, and microplastics (MPs) as particulate contaminants in a riverine basin.
In the first part of the study (Chapter III), PFAAs were characterized in indoor dust samples across diverse indoor micro-environments (laboratories, offices, dormitories, and classrooms) in Tainan, Taiwan. Results revealed significant spatial heterogeneity, with laboratories (median ΣPFAAs: 528.9 μg/kg) and offices (median ΣPFAAs: 304.2 μg/kg) identified as exposure hotspots compared to dormitories (median ΣPFAAs: 180.1 μg/kg) and classrooms (median ΣPFAAs: 105.1 μg/kg). Crucially, the application of stepwise cluster analysis challenged the traditional theory that relies solely on organic carbon (TOC) partitioning. This study demonstrated that PFAA accumulation in indoor dust is not dominated by TOC content but is controlled by moisture content and cation content through electrostatic interactions and interfacial adsorption. Health risk assessments indicated that while overall risks were acceptable (Hazard Quotient < 1), chronic exposure via dust ingestion remains a concern in high-occupancy environments.
Building on Chapter III, the second part (Chapter IV) further elucidated the dialectical relationship between organic carbon quality and quantity in PFAAs sorption. Batch and column experiments compared two high-carbon amendments: peat and composted swine manure (CSM). Results showed that despite having lower TOC content than peat, CSM exhibited significantly higher sorption affinity and retardation for long-chain PFAAs. This study demonstrated that microscopic pore architecture ("narrow throat" entrapment effect) and specific functional group composition (nitrogenous groups) are the key determinants of PFAAs retardation, rather than total carbon quantity alone.
The third part of the study, Chapter V, characterizes the spatiotemporal distribution of MPs in the Yanshui River Basin through a year-round monitoring campaign. MPs were ubiquitous (detection frequency 100%), with surface water abundance averaging 235.1 items/L, while riverine sediment (average 20,370 items/kg) served as a major sink, accumulating concentrations 1-2 orders of magnitude higher than in surface water. Redundancy analysis identified agricultural land use as a primary driver for surface water pollution. A distinct seasonal "flush and fill" regime was observed: wet season flows mobilized MPs (flush), while dry season low-flows facilitated the deposition of denser polymers into sediments (fill). Furthermore, this study highlighted a critical "Abundance-Risk Disconnect." While abundance-based metrics (Pollution Load Index) suggested low risk, toxicity-based metrics (Polymer Risk Index) revealed high ecological risks driven by hazardous polymers like PVC and PU, underscoring the necessity of polymer-specific risk assessment.
Integrating these findings, this study concludes that PFAAs are controlled by physicochemical interactions (electrostatics, moisture, and organic matter quality), while MPs in riverine sediments are influenced by basin-scale hydrodynamic drivers (seasonal flow/land use). These insights advocate for a shift in environmental management strategies from simple concentration monitoring to control based on organic matter characteristics and polymer toxicity, to effectively mitigate the risks of "forever chemicals" and plastic pollution in solid environmental matrices. Overall, this study demonstrates that solid environmental matrices, including dust, amended soils, and riverine sediments, play a critical role as sinks for the retention, transport, and risk expression of persistent contaminants, emphasizing the need to incorporate matrix-specific mechanisms into future fate assessment and environmental management frameworks.

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