全氟烷基化合物 (Perfluoroalkyl substances, PFAS)廣泛應用於潤滑劑、拋光劑、黏合劑、農藥、去污劑、紙張和紡織品塗料等產品中。研究顯示，PFAS可能經由生產、儲存、運輸、工業應用、產品使用及廢棄之過程中釋放至環境，且由於PFAS具有環境持久性，可長時間存在並累積於各種環境介質中，進而透過長程傳輸特性，將污染傳至遠方環境，最後經由食物鏈及食物網之生物濃縮及生物放大作用，累積在生物體內，對環境及生物造成威脅及影響人類健康。因此，斯德哥爾摩公約分別於2009年及2019年將全氟辛酸 (Perfluorooctanoic acid, PFOA)及全氟辛烷磺酸 (Perfluorooctanoic acid, PFOS)納入持久性有機污染物 (Persistent organic pollutants, POPs)列管名單中，歐盟亦基於水框架指令 (Water Framework Directive, WFD)，將PFAS列為優先有害物質；歐洲化學總署 (European Chemicals Agency, ECHA)亦將PFAS列入高度關注物質 (Substance of very high concern, SVHC)清單中，各國亦陸續開始管制PFAS。目前台灣對於各種環境介質中PFAS的濃度分布缺乏深入、完整之調查，且河川環境是各種環境污染物之最終沈積處。因此，本研究主要目的為建置河川底泥及魚體中20種PFAS同源物之前處理及分析方法，並以建置完成之前處理及分析方法，針對台灣主要河川枯、豐水期之底泥及魚體中20種PFAS同源物濃度進行調查，最後綜合所有數據估算台灣河川中PFAS之生物-底泥累積係數 (Biota/Sediment Accumulation Factors, BSAFs)，以瞭解PFAS在台灣河川環境之分布及生物濃縮特性。
本研究於2020年枯、豐水期採集台灣地區15條主要河川之底泥及魚體樣本。樣本進行冷凍乾燥及均質後，保存於4 ℃。底泥樣本先進行鹼性消化，再以甲醇、乙腈之混合溶液進行萃取，魚體樣本則取萃取後上清液再添加正己烷以去除油脂，兩種樣本皆以Oasis® WAX管柱淨化，將流洗液濃縮、定量後，以LC-MS/MS上機分析。其樣本前處理測試之底泥淨土20種PFAS同源物基質添加回收率介於50.1-122.5 %，而魚體20種PFAS同源物基質添加回收率介於45-132.5 %。
本研究於15條台灣主要河川枯、豐水期共採集120個底泥及45個魚體樣本，其樣本分析結果顯示，底泥樣本中20種PFAS同源物總平均濃度及範圍為2.25 μg/kg dw (1.653-4.988 μg/kg dw)，以南部將軍溪4.988 μg/kg dw最高，北部基隆河3.255 μg/kg dw次之，南部八掌溪1.653 μg/kg dw最低。15條主要河川中除了北部淡水河本流及基隆河，其他河川皆以PFCA總平均濃度高於PFSA總平均濃度。依河川地理位置劃分北、中、南、東四地區，結果顯示，四地區皆以PFCA總平均濃度高於PFSA總平均濃度。在20種PFAS同源物濃度分布中，15條主要河川分別以PFOS、PFPeS、PFHxDA為主要化合物。枯豐水期底泥濃度相比，除了PFHxDA及PFNS，其他化合物皆以枯水期濃度高於豐水期濃度，且兩季底泥濃度呈顯著差異 (p<0.001)，可能受到底泥與水交互作用及環境條件影響。關於PFAS可能排放源的評估結果顯示，河川底泥PFAS總平均濃度與河川前十大主要事業別之許可放流水總量呈顯著相關性 (R² = 0.5497, p<0.05)，亦與污水處理廠放流水水量呈顯著正相關 (R² = 0.5144, p < 0.01)，顯示污水處理廠相關程序對處理PFAS成效有限。
魚體樣本中20種PFAS同源物總平均濃度及範圍為5.74 μg/kg ww (3.09-9.71 μg/kg ww)，以南部將軍溪9.71 μg/kg ww最高，東部花蓮溪8.28 μg/kg ww次之，南部林邊溪3.09 μg/kg ww最低。在各魚種濃度中，PFCA、PFSA及PFAS總平均濃度皆以海鰱仔最高分別為5.02、5.04及10.06 μg/kg ww且多數河川魚體以PFOS為主要化合物，顯示PFOS具生物累積潛力。本研究魚體樣本以吳郭魚為大宗，以吳郭魚之log PFAS平均濕重濃度與平均體長呈顯著正相關 (R² = 0.2308, p < 0.05) ，可能有生物累積的情形產生。在底泥及魚體中PFAS同源物濃度皆以PFOS最高且兩介質PFAS濃度呈顯著正相關 (R² = 0.4119, p < 0.05) ，顯示底泥濃度亦可能會影響魚體濃度。在主成分分析中，底泥及魚體成分分析結果位在同一個象限，且對照因子分布發現化合物PFOS及PFUnA也在相同象限，指出兩介質中PFAS同源物之PFOS及PFUnA濃度呈現正相關，說明魚體PFOS及PFUnA的濃度可能來自底泥濃度的轉移。所有魚種在PFCA之BSAF皆大於1且魚體濃度與BSAF呈顯著正相關 (R² = 0.7235, p < 0.05)。而浮游性魚類多數PFAS同源物之BSAF皆高於底棲性魚類，初步推測可能由於本研究採集之樣本以吳郭魚種為大宗，雖然此魚種歸類為浮游性，但其適應力強又食性為雜食性，可能容易經由食物鏈進行生物累積，導致浮游性魚類BSAF高於底棲性魚類。

Perfluoroalkyl substances (PFAS) are widely used in many kinds of industrial and commercial products. PFAS have three environmental characteristics, including persistent in the environment, the potential for long range transporting, and bioaccumulation. However, little is known about the profile of PFAS in the river environment in Taiwan. The present study is aimed to establish the pretreatment procedure/analytical method including quality assurance and quality control for measurement of 20 PFAS congeners in sediments and fishes, and then use to investigate the levels of PFAS in sediments and fish during dry and wet seasons of the 15 principal rivers in Taiwan. Finally, all the data were integrated to calculate the Biota/Sediment Accumulation Factors (BSAF) and to realize the bio-concentration and bioaccumulation characteristics of PFAS in the river environment around Taiwan.
One hundred and twenty sediment samples and forty-five fish samples are collected and extracted by solvent extraction, inaddition, the extracts of fish sample were added hexane to remove lipid. The cleanup of PFAS in the sediment and fish samples were performed by Oasis® WAX column, and then using liquid chromatography-tandem mass spectrometry to analyze the PFAS. The average concentration of PFAS in the sediment samples was 2.25 μg/kg dw. The highest level was found in PFOS. The average concentration of PFAS in the fish samples was 5.74 μg/kg ww. The highest level was also found in PFOS. And the highest BSAF was found in PFOS too. The average concentration of PFCA in sediment was higher than PFSA, no matter departed by 15 rivers or 4 regions. The average concentration of PFAS in sediment between two seasons shows significant differance. The sources of pollution for PFAS were related with discharge from industrial classification and sewage treatment plants respectively. The growing situation of fish might resulted in the bioavailability of PFAS increased.

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