由於科技的發達，塑膠已成為日常生活及工業上不可或缺的材料。其中經工業製造和環境降解所形成之塑膠微粒(microplastics)會藉由廢水排放及自然循環累積並散播到世界各處。現今的研究報告多著重於微米級塑膠微粒的研究，但已有研究顯示奈米塑膠微粒(nanoplastics)存在於環境中，不過仍缺乏可信之定性及定量分析方法。本研究的目的擬開發結合飛行時間二次離子質譜儀(time-of-flight secondary ion mass spectrometry, TOF-SIMS)來判斷奈米塑膠微粒之種類及進行顆粒數之半定量分析，與掃描式電子顯微鏡(scanning electron microscope, SEM)來獲得塑膠微粒的粒徑大小、型態及數目的資訊。在定性方法方面，收集海邊塑膠廢棄物與市售商品(材質包括聚乙烯(PE)、聚丙烯(PP)、聚氯乙烯(PVC)、聚對苯二甲酸乙二酯(PET)及聚苯乙烯(PS)以及耐隆66 (Nylon 6,6))，並以TOF-SIMS質譜結合主成分分析法(principal component analysis, PCA)，發現除PP與PE分辨能力不佳外，其餘皆可被有效區分。定量方法方面，發現當305或1040 nm PS奈米塑膠微粒的懸浮液數目濃度≥ 3.56×108 particles/mL的濃度下，線性迴歸係數皆可達0.99以上。在方法驗證部份，混合了實驗室自行合成之3種不同奈米塑膠微粒及PS商業標準品，使用SEM影像進行定量及TOF-SIMS質譜影像進行定性及半定量，可量測四種塑膠微粒之總顆粒數、型態、以及不同塑膠之顆粒數比例。最後實際應用至偵測6個市售茶包以熱水浸泡後釋放之塑膠微粒樣品，並與奈米追蹤分析儀(nano-tracking analysis)之結果進行比較，發現SEM及NTA所獲得粒徑大小相似，皆在163-203 nm之間，但數目濃度SEM比NTA增加2-5倍。並可由TOF-SIMS量測，得知PET/PE混合茶包釋出塑膠成分的顆粒數目比以及微粒成分之確認。綜合本研究之結果顯示此分析方法具有分析環境中奈米塑膠微粒之潛力。

With the advance of science and technology, plastics has become an indispensable material used in daily life. Among them, microplastics are formed by industrial manufacturing and degraded in the environment, which accumulate and disperse around the world through wastewater discharge and natural circulation. Most of current studies focused on the detection of microplastics, below 5 mm to micrometer scale. However, nanoplastics also exist in the environment, there is still a lack of reliable qualitative and quantitative analysis methods. Therefore, the purpose of this study is to develop a detection method for determining nanoplastics in the environment. This study combined time-of-flight secondary ion mass spectrometry (TOF-SIMS) and scanning electron microscope (SEM) to determine various types of nanoplastics and obtained the particle size, morphology and number information quantitatively or semi-quantitatively. In the qualitative analysis, we mainly collected six different types of plastics from the beach and commercial products, including polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polystyrene (PS) and Nylon 66 (Nylon 6,6). Mass spectra deriving from TOF-SIMS were analyzed by principal component analysis (PCA), which PVC, PET, PS and Nylon 6,6 can be distinguished, but PP and PE were poorly distinguished. In the quantitative analysis, it was found that when the number concentration of 305 or 1040 nm PS suspensions is ≥ 3.56×108 particles/mL, the R-square all can reach more than 0.99. In verification part, we mixed three types of nanoplastics (PVC、PET and PE) synthesized in this study and PS standard underlying the combined detection of SEM (for quantitative analysis) and TOF-SIMS (for qualitative and semi-quantitative analysis) to check the applicability of this method. In practice, nanoplastics releasing from the hot water-treated commercial teabags were well determined in comparison with the results of nano-tracking analysis (NTA). The results showed that the particle size obtained by SEM and NTA were similar, between 163-203 nm, but the number concentration of SEM was 2-5 times higher than that of NTA. According to TOF-SIMS measurement, the ratio of plastics particles and the confirmation of particle composition released by PET/PE teabags were obtained. The results of this study showed that this analysis method has the potential to determine nanoplastics in the environment.

中文摘要 i
英文摘要 ii
致謝 iv
目錄 v
圖目錄 vii
表目錄 ix
第一章 前言 1
第二章 文獻回顧 3
第一節 塑膠微粒 3
一、塑膠微粒的定義及來源 3
二、塑膠微粒進入環境與擴散之途徑 4
第二節 對環境生物及人類之影響 5
第三節 塑膠微粒檢測方法 7
第四節 奈米塑膠微粒與檢測技術 9
第五節 使用之儀器與分析方法 12
一、二次離子質譜儀(Secondary ion mass spectrometry, SIMS) 12
二、掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 14
三、主成分分析法(Principal Component Analysis, PCA) 15
第三章 研究目的與架構 16
第一節 研究目的 16
第二節 研究架構 18
第四章 材料與方法 19
第一節 藥品與樣品 19
一、塑膠標準品 19
二、茶包樣品 19
三、實驗藥品 20
第二節 使用設備 20
一、器材 20
二、儀器 20
三、分析軟體 21
第三節 實驗方法與步驟 22
一、塑膠微粒定性方法開發 22
二、奈米塑膠微粒定量方法開發 26
三、奈米塑膠微粒定性及定量方法驗證 28
四、真實樣品實驗(茶包塑膠微粒溶出實驗) 33
第五章 結果與討論 35
第一節 奈米塑膠微粒合成 35
一、PVC奈米微粒製備 35
二、PET奈米微粒製備 39
三、PE奈米微粒製備 42
第二節 奈米塑膠微粒定量、定性方法及驗證 51
一、定量方法開發 51
二、定性方法之開發 59
三、定性及定量方法之驗證 73
第三節 真實樣品分析-茶包塑膠微粒溶出試驗 78
一、茶包之定性分析 78
二、茶包釋放塑膠微粒之定量分析 81
三、TOF-SIMS 質譜表面影像定性及半定量分析 92
第六章 結論 98
一、本研究之結論 98
二、未來展望 100
參考文獻 102

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