本研究，以螢光衰減法針對多種的腐植酸與一種含氮的三環PAHs（benzo(h)quinoline）的結合係數進行量測，此外以另外一種三環的parent-PAHs（phenanthrene）的結合係數作為對照，並且探討pH值及離子強度對於KCOC的影響進行研究。由研究結果顯示，越趨向高pH值時，由於腐植酸的疏水性會逐漸減弱，因此藉由疏水性作用（hydrophobic interaction）與腐植酸結合的phenanthrene之KCOC值會隨著pH值的增加有下降的現象。benzo(h)quinoline的KCOC值隨pH值變化趨勢，在接近benzo(h)quinoline的pKb附近會有KCOC的最大值。當pH值低於pKb時，benzo(h)quinoline會變成一種質子化的陽離子狀態，稱之為benzo(h)quinolinium，在此區域主要的結合機制為離子交換作用（ion exchange interaction），此時當pH值增加時會存在較多的吸附位基，因此使得KCOC值會隨著pH值而增加；當pH值大於pKb時則會受到不同機制的主導，中性型態的benzo(h)quinoline此時為主要優勢物種，結合機制也轉變成了疏水性作用。由於不同pH值下， 主要優勢物種會有所不同，以單一波長量測，對於KCOC值無法做全程的觀測，因此藉由兩組不同波長的同時量測螢光值以求得較為準確可信的KCOC值。此外，在探討pH值對不同HA與PAHs間KCOC之影響時，也發現HA官能基組成亦為一種影響因素。最後對於離子強度的影響進行初步的探討，由結果顯示加入離子強度後benzo(h)quinoline的KCOC值會降低，但隨pH值的變化仍有相同的趨勢存在。藉由本研究之結果，對於疏水性有機污染物在水體環境中的傳輸與宿命能夠提供給數值模擬上重要的參數。

In this study, we measured the binding constant, KCOC, between several humic acids and benzo(h)quinoline, a nitrogen contained PAHs via using fluorescence quenching method. KCOC of humic acids and phenanthrene, a parent PAHs, is also studied in comparison. Moreover, pH and ionic strength effect on the KCOC were investigated. According to our results, the phenanthrene’s KCOC decreases as the pH increases due to the lower hydrophobicity of humic acid in higher pH values. The variation of benzo(h)quinoline’s KCOC with pH exhibits a more complicated trend, with a maximum value at pH close to the pKb of benzo(h)quinoline. For pH lower than pKb, benzo(h)quinoline is protonated to be benzo(h)quinolinium, a cation, so that the ionic exchange is the dominant prosess in sorption mechanism. Therefore, the binding sites of humic acid increase with pH such that the KCOC increases with pH. In contrast, different mechanism involved in the binding for pH higher than pKb, neutral benzo(h)qunoline becomes dominant and hydrophobic interaction controls the binding prosess in sorption mechanism. At last, the composition of different functional groups of humic acid is also found significant in the binding affinity of benzo(h)qunoline or phenanthrene. Moreover, the benzo(h)qunoline’s KCOC exhibits decreasing trend with increasing magnesium ionic strength because of the reduction of molecular size as well as the benzo(h)qunoline binding sites of humic acid. Findings from this study could provide valuable information for numerical simulation of transport and fates of HOPs in aquatic environment.

目 錄
中文摘要 Ⅰ
英文摘要 Ⅱ
目錄 Ⅲ
圖目錄 Ⅵ
表目錄 Ⅷ
附表目錄 Ⅸ
符號說明 XI


第一章 前言 1
第二章 文獻回顧 4
2-1 膠體性有機物 4
2-2 腐植質 5
2-3 疏水性有機污染物 7
2-4 多環芳香烴碳氫化合物 9
2-5 水環境因子對HOPs吸附行為之影響 10
第三章 實驗材料及方法 15
3-1 實驗材料 15
3-2 實驗方法 17
3-2-1 實驗方法的選用 17
3-2-3 螢光理論校正公式 20
3-3 實驗步驟 21
第四章 結果與討論 24
4-1 螢光衰減法之建立 24
4-1-1 螢光衰減動力學 24
4-1-2 腐植酸溶解動力學 27
4-1-4 螢光衰減法的之適用性 28
4-2 pH值對phenanthrene之KCOC的影響 29
4-2-1 pH值對phenanthrene-LHA結合係數的影響 29
4-2-2 pH值效應對phenanthrene-SHHA結合係數的影響 31
4-2-3 腐植酸種類對phenanthrene之KCOC之影響 32
4-3 pH值效應對benzo(h)quinoline之KCOC的影響 34
4-3-1 不同種類PAHs與腐植酸結合機制之比較 34
4-3-2 benzo(h)quinoline-HA之KCOC隨pH值變化的趨勢 37
4-3-4 高pH值下不同種類腐植酸對KCOC影響機制 47
4-3-5 低pH值下不同種類腐植酸對KCOC影響機制 49
4-4 離子強度的效應 52
4-4-1 離子強度效應於PAHs-COC結合係數的討論 52
4-4-2 腐植酸與鎂離子反應動力學 53
4-4-3 離子強度對benzo(h)quinoline之KCOC的效應 55
4-4-4 本實驗數據與相關文獻比較 57
第五章 結論與建議 59
5-1 結論 59
5-2 建議 61
參考文獻 62
附錄 70

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