戴奧辛類化合物為目前已知毒性最強的致癌性化學物質之一，現階段受中低濃度戴奧辛污染土壤缺少較合適處理方式，化學氧化法是透過氧化劑與污染物接觸進而破壞污染物的處理技術，具有效率高和可實場操作之潛力。然而氧化劑和有機污染物異相間質量傳輸的障礙往往成為化學氧化法效果的限制因子，本研究嘗試利用Triton X-100、Tween 80作為界面活性劑，十二烷基苯磺酸鈉(SDBS)作為輔劑以增加戴奧辛類化合物之水溶性，並使用過碳酸鈉(Sodium percarbonate, Na2CO3•1.5H2O2)和過硫酸鈉(Sodium persulfate, Na2S2O8)作為氧化劑，以化學氧化法結合界面活性劑處理毒性當量為141,000 ng I-TEQ/kg受戴奧辛污染土壤，評估適用反應條件與接續生物處理之可能性，期望能有效去除土壤中戴奧辛類化合物。研究結果顯示以SDBS取代部分非離子性界面活性劑能有效提升從土中溶出OCDD的能力，Tween 80因為結構不相似於OCDD，使其對於OCDD之增溶能力不佳，Triton X-100對於OCDD的增溶效果優於Tween 80，而Triton X-100：SDBS為7：3的界面活性劑有最好的增溶效果，在濃度20g/L時可溶出25%之OCDD至水相之中。此外，系統中OCDD/F去除效果最好之氧化劑配比依序為使用50mM的0:1、3:1、2:1氧化劑(過碳酸鈉：過硫酸鈉)，但考量氧化劑的特性，選用3:1為最佳配比，對OCDD去除率可達60%，對OCDF去除率可達36%。將最佳配比應用於土壤後，總毒性當量降低至83,500 ng I-TEQ/kg，毒性當量去除率為40.7%，證實為界面活性劑結合化學氧化法為具有潛力的整治方法。

Chemical oxidation is a common treatment in soil organic pollution which has a high removal rate and short remediate duration. Although it has many advantages, the heterophase between oxidant and pollutant will often become a limitation to removal efficiency. Therefore, Triton X-100, Tween 80 and sodium dodecylbenzenesulfonate (SDBS) were used as surfactant to enhance the solubility of PCDD/Fs. In addition, sodium percarbonate (SPC) and sodium persulfate (Na2S2O8) were used as oxidant. By combining the reagents, it is expected that the chance of PCDD/Fs oxidation would raise thus the increases the removal rate.

The results showed that the PCDD/Fs concentration in liquid phase raised when surfactants were added in the contaminated soil. Furthermore, the results also showed that replaced certain level of Triton X-100 and Tween 80 with SDBS would increase the solubilization ability of surfactant. When the mass ratio between Triton X-100 and SDBS equals to 7:3 and the concentration of surfactant is 25g/L, 25% of OCDD would be partitioned into liquid phase, which had the best performance. The oxidation experiment results showed that using 50mM of Na2S2O8 and mixed oxidant (SPC: Na2S2O8 = 3:1, C3S1) had the highest OCDD/F removal rate. Considering the toxicity of oxidants, C3S1 was chose as the best oxidant. After applying it in a larger batch test, the toxicity equivalent concentration in soil had decreased 40.7% from 141,000I-TEQ ng/kg which indicated that treating PCDD/Fs contaminated soil by surfactant-enhanced chemical oxidation is a method with development potential.

摘 要 I
誌 謝 VI
目 錄 VIII
表目錄 XI
圖目錄 XIII
第一章 前 言 1
1-1研究動機與目的 1
1-2研究內容 2
第二章 文獻回顧 4
2-1持久性有機污染物之特性概述 4
2-1-1持久性有機污染物之基本特性 4
2-1-2戴奧辛之基本特性 7
2-1-3戴奧辛污染場址案例 11
2-2土壤污染整治技術 17
2-2-1通用土壤污染整治技術 17
2-2-2土壤重金屬污染整治技術 19
2-2-3土壤有機污染整治技術 20
2-3現地化學氧化技術 24
2-3-1現地化學氧化之簡介 24
2-3-2過碳酸鹽氧化法的原理及應用 30
2-3-3過硫酸鹽氧化法的原理與應用 35
2-3-4影響過碳酸及過硫酸鹽氧化反應之因子 39
2-4土壤淋洗/清洗技術 50
2-4-1界面活性劑之簡介 50
2-4-2界面活性劑於土壤淋洗/清洗技術原理與應用 53
2-4-3影響淋洗/清洗效果之因子 61
2-5小結 64
第三章 研究材料、設備與方法 66
3-1研究架構與流程 66
3-2研究材料與設備分析 69
3-2-1受戴奧辛污染土壤前處理 69
3-2-2實驗試藥 69
3-2-3儀器設備 70
3-3實驗設計與分析方法 75
3-3-1臨界微胞濃度之測定方法 75
3-3-2 OCDD於土水相分布測定實驗 77
3-3-3受戴奧辛污染土壤之氧化實驗 78
3-3-4受戴奧辛污染土壤之批次降解實驗 78
3-3-5受戴奧辛污染土壤之浸泡式管柱降解實驗 79
3-3-6 分析方法 81
第四章 結果與討論 85
4-1受污染土壤基本特性與臨界微胞濃度 85
4-1-1受戴奧辛污染土壤之基本特性 85
4-1-2界面活性劑之臨界微胞濃度 92
4-1-3 小結 99
4-2界面活性劑對受污染土壤之清洗效果 100
4-2-1界面活性劑混合比例對於OCDD水相濃度的影響 100
4-2-2界面活性劑濃度對於OCDD分布的影響 103
4-2-3界面活性劑對OCDD於土水相分布的影響 107
4-2-4小結 110
4-3不同氧化劑配比處理土壤中OCDD/F之效果 111
4-3-1氧化劑混合比例對於OCDD/F去除效果的影響 111
4-3-2氧化劑濃度對於OCDD/F去除率的影響 119
4-3-3反應後系統OCDD/F之殘留濃度和去除率 128
4-3-4小結 130
4-4界面活性劑結合化學氧化法處理受戴奧辛污染土壤之效果 132
4-4-1戴奧辛種類及濃度之去除率 132
4-4-2 浸泡式管柱反應器處理受戴奧辛污染土壤之效果 134
4-4-3 小結 138
第五章 結論與建議 140
5-1結論 140
5-2建議 142
參考文獻 143

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