本研究係利用尺寸為60 cm×30 cm×30 cm(長×寬×高)之砂箱實驗模擬電動力現地處理受酚污染之土壤。土體分為飽和層及未飽和層，進行20天之電動力實驗，藉由不同電場條件、轉換電極極性、電極槽添加Fenton試劑等操作條件，探討在電動力過程中及處理後土體相關參數、電場及污染物殘留等的分布情形。研究結果發現，在不進行電極極性轉換的電動力實驗組中，其陽極槽液pH值在施加電場2 ~3天後即降至2左右，陰極則上升至12左右，此現象持續至實驗終了；於轉換電極極性的實驗中，陽、陰極槽液的pH值變化則較不明顯（陽極槽液pH 4、陰極槽液pH 11）。
由陰、陽電極兩端間之土體孔隙水pH值變化得知，不論於定電壓或定電流系統中，電動力反應進行過程陰、陽極端產生之鹼、酸鋒會隨時間增加而各自往土體另一端方向移動，且初期鹼鋒移動速度較快而酸鋒移動速度較慢，惟實驗結束後，不論飽和層或未飽和層，其中段土體仍呈中性，並未受到酸、鹼鋒明顯的影響。
於定電壓(50 V)、不進行電極極性轉換的操作條件下，電動力或電動力-Fenton的實驗進行過程中，土體相對於陰極之電壓差變化於反應初期約呈線性關係，而後隨處理時間增加而呈非線性關係；而在電極極性轉換的實驗中，由於在酸、鹼鋒形成電阻極化之前便進行電極極性轉換，因此，並無明顯的電壓差變化。
於定電壓或定電流系統之電動力處理過程中，未飽和層土壤之含水率雖受到毛細現象影響而升高，但由於其土體並未直接與電極槽液接觸，電動力工法之電滲透效應對未飽和層的土壤含水率影響相對較小，導致反應後未飽和層之含水率反而較反應前為高，由25.34%上升至30%左右。在電滲透流率大小方面，由於轉換電極極性的實驗中，在兩電極槽皆可收集排出液的情況下導致其電滲透流量最大，於定電壓及定電流操作下，其電滲透係數分別為6.42×10-6 cm2/V•s及9.47×10-6 cm2/V•s。其次為沒有添加酚於土壤中之實驗組，其電滲透係數為3.27×10-6 cm2/V•s，由此可知，污染物的存在的確會阻礙電滲透流的傳輸。至於添加Fenton試劑之電動力實驗組的電滲透係數則較未添加Fenton試劑之實驗組為大，定電壓下其電滲透係數分別為1.59×10-6 cm2/V•s及9.45×10-7 cm2/V•s，定電流下則分別為2.31×10-6 cm2/V•s及9.50×10-7 cm2/V•s。在處理效率方面，不論於定電壓或定電流系統中皆以電動力-Fenton法實驗組最佳，酚的總破壞去除率分別為78.06%及80.11%，其次為不添加Fenton試劑之電動力實驗組，總破壞去除率分別為69.92%及71.38%，而電極極性轉換實驗組之總破壞去除率則較不理想，僅62.34%~64.30%。造成轉換電極極性的實驗組效果不佳之原因，可能係由於電動力對於酚之破壞效應小於酚受電滲透移除效應影響之故，酚在未移出土體之前即由於轉換電極極性而導致停滯於土體中，此結果可由轉換電極極性的實驗組實驗後土體中段土壤中酚殘餘量高於其他段土體而知。

The purpose of this study was to evaluate the treatment efficiency of phenol contaminated soils by electrokinetic (EK) process conducted in sand boxes (60 cm×30 cm×30 cm; L×W×H). The electric field strength, electrode polarity reverse, and Fenton reagent were employed as the experimental factors in this study to assess the variations of soil characteristics, potential difference, and residual phenol concentration distribution during a treatment period of 20 days and after the treatment. It was found that the anode reservoir pH decreased to around 2 and the cathode reservoir pH increased to approximately 12 after 2~3 days of treatment in the no electrode polarity reverse system. However, the variation of pH in the anode and cathode reservoirs was less obvious in the case with electrode polarity reverse.
No matter a constant potential system or a constant current system was employed, a general trend of a lower pH at the anode reservoir and a higher pH at the cathode reservoir would be found. The acid front generated at the anode reservoir flushed across the soil specimen toward the cathode and the base front advanced toward the anode. However, in the central region of sand box, unsaturated and saturated soil specimen maintain neutral.
For EK or EK-Fenton experiments, under the constant potential conditions, the potential difference relative to the cathode versus the distance from anode was found to have a linear relationship at the beginning of the electrical potential application. As the treatment time elapsed, the potential gradient became non-linear. Nevertheless, there was no remarked potential gradient change in the case with electrode polarity reverse.
Although capillarity has resulted in an increase of the moisture content of unsaturated soil (from 25.34% to 30% after 20 days), electroosmotic (EO) flow was not obvious in the unsaturated zone.
For the experiments with electrode polarity reverse, they had a much greater EO flow quantity, the electroosmotic permeability coefficients for constant potential and constant current systems were 6.42×10-6 cm2/V•s and 9.47×10-6 cm2/V•s, respectively. It was also found that the existence of contaminants did reduce the EO flow quantity.
Regardless of the employment of a constant potential or constant current system, the maximum destruction and removal efficiency (DRE) of phenol was obtained for EK-Fenton process. The maximum DRE values of phenol for both constant potential and constant current systems were found to be 78.06% and 80.11%, respectively. However, the DRE of phenol was found to be much lower for the system with electrode polarity reverse. It was postulated that the destruction efficiency of phenol was less obvious than the removal efficiency in the electrode polarity reverse system. In addition, a frequent reverse of electrode polarity also resulted in a frequent change of EO flow direction. Thus, a flow hysteresis of phenol in the soil compartment was found.

目 錄
頁次
謝誌 i
摘要 ii
Abstract iv
目錄 vi
表目錄 ix
圖目錄 x
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 5
1.3 研究內容 5
第二章 基本理論與文獻回顧 6
2.1 酚之基本性質及危害性 6
2.2 酚於土壤中之傳輸機制與吸附特性 10
2.3 電動力法之相關理論 11
2.3.1 電動力法傳輸及反應機制 11
2.3.2 電動力法之極化現象 13
2.3.3 電動力法之影響因子 14
2.3.4 電動力法的優點 16
2.4 電動力法處理污染物之相關研究 18
2.4.1 電動力法處理有機污染物之相關研究及案例 18
2.4.2 電動力法二維模場之相關研究 19
2.4.3 電動力法結合其它方法之相關研究 20
2.5 Fenton法之反應機制 22
第三章 實驗材料、方法與架構 32
3.1 實驗材料 32
3.1.1 土樣來源與前處理 32
3.1.2 試藥及材料 32
3.2 實驗設備 36
3.2.1 電動力法處理系統 36
3.2.2 其它儀器設備 38
3.3 研究架構 40
3.4 土壤樣品基本性質分析 44
3.4.1 pH值 44
3.4.2 含水份 44
3.4.3 比重 45
3.4.4 有機物含量 47
3.4.5 灼燒減量 47
3.4.6 陽離子交換容量 47
3.4.7 粒徑分析 48
3.5 人工污染土配製及砂箱裝填 50
3.5.1 人工污染土配製程序 50
3.5.2 污染土砂箱裝填程序 50
3.6 電動力反應前後及過程分析 51
3.6.1 電動力處理前後分析 51
3.6.2 電動力處理過程監測分析 52
第四章 結果與討論 54
4.1 土壤樣品基本性質分析 54
4.1.1 pH值 54
4.1.2 含水份 54
4.1.3 比重 54
4.1.4 有機物含量 54
4.1.5 灼燒減量 54
4.1.6 陽離子交換容量 54
4.1.7 粒徑分佈 55
4.1.8 比表面積 56
4.2 定電壓-電動力法處理受酚污染之土壤 57
4.2.1 電動力處理過程分析 57
4.2.2 電動力處理後分析 67
4.3 定電壓-電動力-Fenton法處理受酚污染之土壤 73
4.3.1 電動力處理過程分析 73
4.3.2 電動力處理後分析 83
4.4 定電壓-電動力法-電極極性轉換處理受酚污染土壤 89
4.4.1 電動力處理過程分析 89
4.4.2 電動力處理後分析 98
4.5 定電流-電動力法處理受酚污染土壤 104
4.5.1 電動力處理過程分析 104
4.5.2 電動力處理後分析 111
4.6 定電流-電動力-Fenton法處理受酚污染之土壤 117
4.6.1 電動力處理過程分析 117
4.6.2 電動力處理後分析 123
4.7 定電流-電動力法-電極極性轉換處理受酚污染土壤 129
4.7.1 電動力處理過程分析 129
4.7.2 電動力處理後分析 135
4.8 綜合討論 141
4.8.1 電極質量變化 141
4.8.2 電滲透流探討 143
4.8.3 處理效率探討 145
4.8.4 經濟效益評估 147
第五章 結論與建議 150
5.1 結論 150
5.2 建議 153
參考文獻 154
附錄 實驗數據 167

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