摘 要

疏水性有機污染物在環境中不易分解，具有毒性及高生物累積性，因此其宿命與傳輸機制一直為學界研究重點。由於其疏水性質，疏水性有機污染物在環境中的傳輸宿命以吸附行為為主，但除了一般認知的水－顆粒兩相間的吸附現象以外，溶解性有機物的參與無疑使整個吸附機制更形複雜，卻也更接近真實環境中疏水性有機物的實際吸附行為。

在目前各相關領域中，對疏水性有機污染物與溶解性有機物的結合機制各家說法不一，但所有研究在其實驗設計上都脫離不了對平衡的假設。von Wandruszka, Ragle, and Engebretson, （1997）; Engebretson and von Wandruszka, （1998）等人提出，HOPs、DOM與金屬陽離子間的反應是緩慢、可逆甚至是擺盪（oscillating）的動力學，此一現象會影響到實驗的再現性與否，以及對數據的解釋。因此本研究以螢光衰減法對pyrene注入HA溶液中之平衡反應動力學進行一系統化的研究。

本研究發現pyrene在HA溶液中螢光值的變化，主要分成兩個階段：一開始受到pyrene擴散分佈以及pyrene與HA分子反應的影響，螢光值迅速下降，其中又以前者為主要的控制因子；而後，則因為瓶壁吸附pyrene的作用使螢光值緩慢下跌。Pyrene分子在HA溶液中的散佈速率主要受HA分子大小以及HA分子數量多寡所控制，當離子強度提高，所添加的陽離子造成HA分子結構的捲曲縮小，減少pyrene分子在擴散階段所遭受的阻力，使得擴散速率常數變大，當系統中HA分子數量變小時也有著相同的結果。離子強度可能造成pyrene與HA發生鹽析作用，除了使pyrene瓶壁效應更加明顯外，同時也促使pyrene與HA間的疏水性鍵結更趨穩固；在本研究中所得到的結果，後者效應應大於前者。

至於在本研究之Mg2+-LHA系統中，並沒有觀察到所謂鎂離子「游移」（migration）在LHA分子中、需長時間方能安定的結果；造成與E & W等學者實驗結果不同之因，推論應為HA種類不同所致，也因此Engebretson and von Wandruszka等學者的實驗結果，並不能直接對其他文獻所得的結果提出質疑或反駁。

此外，本研究並以Mg2+、Ca2+、Sr2+等不同陽離子進行pyrene與LHA結合係數的研究。離子強度造成pyrene與LHA結合係數Kdom的變化，主要肇因於腐植酸在陽離子介入後結構與性質發生變化所致，而各種陽離子與腐植質上不同的吸附位基有著不同的反應性，不同陽離子對Kdom便有著不同的影響。因此Mg2+、Ca2+、Sr2+等不同陽離子除其電荷密度的差異造成對HA分子上負電性官能基有著不同的鍵結能力以外，各種陽離子與腐植質上不同的吸附位基間不同的反應性亦不能忽視。

ABSTRACT

Hydrophobic organic pollutants (HOPs) are in general characterized by high toxicity, long environmental half-life and high bio-accumulation factors. Due to their hydrophobicity, HOPs tend to sorb onto particles in environment. The influence of the dissolved organic matters (DOMs) on the sorption partition coefficient is observed because of their interactions with HOPs. This binding between DOM and HOPs increases apparent solubility and mobility of the HOPs in natural aquatic system. On the purpose of obtaining data closer to the real world, many aquatic factors, such as the concentration and types of DOM, pH value and ionic strength, are studied intensively recently.

There are many studies about the mechanisms in the association of DOM and HOPs. Most of them assume achievement of equilibrium in their measurement. Recently, it was reported (Engebretson and von Wandruszka, 1998) that slow, revering, and even oscillating kinetics are observed. It is great concern and interest to those related studies in literatures. Complicated kinetic may in fact be a cause of the reproducibility problems for measurements of HOPs associated with both humic acid and metals. As such, by monitoring fluorescence intensity, we investigate the equilibrium kinetic of pyrene in HA solutions.

In this study, results show that there are two stages of the fluorescence intensity after pyrene spiked into HA solutions: First, the fluorescence intensity decreases steeply due to the first dispersion of pyrene and the reaction of pyrene and HA (the front is dominance). Secound, fluorescence intensity decreases gently because of wall-effect. The dispersion rate of pyrene in HA solutions is difference with HA molecular size and quantity. As the ionic strength rising, cations reacting with specific binding sites on HA, the molecules’ configuration of HA is changed, and less obstruct for dispersing of pyrene. It works as well as little molecular quantity. For second stage when ionic strength rising, wall- associations is less because of the hydrophobic-binding of pyrene and LHA is more stronger.

Furthermore, it is not observed the “migration” of Mg2+ within the LHA molecular structure as described by Engebretson and von Wandruszka .The reasons that make different results may depend on the species of humic acid. Therefore, the observations of Engebretson and von Wandruszka could not be used directly questioning those results in literatures.

In addition, the effects of various cations (Mg2+, Ca2+and Sr2+) on Kdom are studied. It is believed different cation reacts with different specific binding sites on HA. As such, both charge density and affinity of cation with specific binding sites on HA should be considered in discussing the effects of metal ionic on the binding constants between PAHs and DOM.

第一章 前言 1
第二章 文獻回顧 3
2-1 溶解性有機物 3
2-1-1何謂溶解性有機物? 3
2-1-2腐植質概述 4
2-2 疏水性有機污染物 7
2-2-1疏水性有機污染物概述 7
2-2-2多環芳香烴化合物 8
2-3 HOPs之吸附行為文獻回顧 12
2-3-1 研究進程 12
2-3-2 水環境因子之影響 13

第三章 實驗材料及方法 16
3-1 實驗材料 16
3-2 實驗方法 17
3-2-1 實驗方法的選用 17
3-2-2 螢光衰減法原理概述 19
3-2-3 校正公式 21
3-3 實驗步驟 23
3-3-1 螢光衰減實驗步驟 23
第四章 結果與討論 25
4-1 瓶壁效應 25
4-2 影響平衡動力學因素之探討 25
4-2-1 不同HA濃度的影響 28
4-2-2 不同離子強度的影響 31
4-2-3 不同陽離子種類的影響 35
4-2-4 不同HA種類的影響 40
4-2-5 平衡動力學模式綜合討論 45
4-3 螢光衰減法實驗步驟之確立與應用 47
4-3-1 螢光衰減理論應用之確立 48
4-3-2 螢光衰減法趨勢線之應用 50
4-4 平衡動力學上的疑點 57
4-4-1 鎂離子與LHA的平衡時間 58
4-4-2 實驗系統上的差異 58
第五章 結論與建議 65
5-1 結論 65
5-2 建議 67
參 考 文 獻 69
附 錄 77

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