臺灣博碩士論文加值系統

隨著工業進步的過程中，近年陸續開始重視土壤及地下水污染的嚴重性。由於受含氯有機溶劑重質非水相液體（Dense Non-Aqueous Phase Liquid，以下簡稱DNAPL）污染場址整治具有相當高之困難度，而傳統整治方式（例如：抽取處理法及空氣灌入法）僅針對溶解相之DNAPL污染進行處理，並無法有效移除DNAPL之污染源，造成整治時程延長及整治經費提高。
堆肥化/液肥之生物整治技術將污染土壤與堆肥/液肥混合接觸，藉由此技術提高微生物活性，促進污染物之降解，且相較於其他技術能降低耗能排碳。過去研究中提出，「液肥」中有許多生物界面活性劑（包含醇、酮、酯以及腐植酸類），生物界面活性劑本身是自然界生成的物質，對環境的影響相對較小，是取代化學界面活性劑的良好選擇；在本研究中，以1, 2-二氯乙烷（1, 2-Dichloroethane，1, 2-DCA或EDC）為目標污染物，進行模擬現地受EDC污染土壤及地下水，再以「液肥」當作生物界面活性劑沖排，並進行可行性的探討。
本研究分別模擬「均勻污染」與「高濃度點源污染」兩種不同污染方式。沖排過程將不同比例之乙醇添加在液肥中，分別為20%與50%，以提高去除效率。結果顯示：（1）試驗前，對「液肥」進行揮發性有機化合物（Volatile Organic Compounds, VOCs）、半揮發性有機化合物（Semi-Volatile Organic Compound, SVOCs）與重金屬的分析檢測，有害物之背景濃度均符合雜項有機液肥管制標準，無二次污染之虞，適合當作本研究及未來現地整治之沖排液使用。（2）「均勻污染」沖排至2 PV時即有明顯之去除效率，增加50%乙醇去除率可達88%，2 PV之後皆呈現平緩趨勢，但對於「高濃度點源污染」需要的時程較長（約5-10 PV）。沖排後之土壤殘餘EDC濃度均符合管制標準（8 mg/Kg）、重金屬含量也無增量。（3）沖排液應用於兩者之去除效率依序皆為：「50%液肥 + 50%乙醇」＞「80%液肥 + 20%乙醇」＞「100%液肥」＞「水」。
以上結果顯示，液肥具有一定之沖排效率，但若添加乙醇沖排效果更佳，建議未來可再改善液肥的製程，以提高液肥中的醇類。若將「液肥」應用於現地整治，殘留於地下之液肥可以充當土壤改良劑，以及微生物之營養源，具有增強自然復育之功效；此技術為節能減碳之綠色整治技術，具環境友善之優勢，故在市場上應有相當程度之競爭力及需求。

In these recent years, the industrial business rapidly grow and develop in the Southern part of Taiwan. Meanwhile, these larger industrial expansion also cause the environmental contaminations with some complex hazardous substances that become the significant and serious problems in this time.
In case of the contamination by Chlorinated Organic compound, the remediation idea to treat a Dense Non-Aqueous Phase Liquid (DNAPL) part of this compound is relatively hard to perform. The results from previously traditional remediation methods which apply to treat the dissolved DNAPL contaminants revealed that the removal efficiency were very low. Moreover, those remediation methods required a longer duration time and high cost for the treatment process. Meanwhile, some study which applied the biological compost or compost tea in their remediation indicated that the microbial activity can be improved by these methods. In addition, these methods could reduce more the energy consumption and carbon emissions, if compare with the other methods. Further significant thing is the biological surfactants, which is the natural substances exist in compost tea that can apply without any side effects on environment. Therefore, the compost tea are also applied on contaminated soil and groundwater flushing process for the 1, 2-dichloroethane removal in this study.
This study was performed by simulation of two conditions of contaminant distribution between the homogeneous contamination and concentrated point source. In the flushing process, the ethanol were added in two different percentages (20% and 50%) to increase the removal efficiency. Compost tea were analyzed for the Volatile Organic Compounds (VOCs), Semi-Volatile Organic Compounds (SVOCs) and heavy metals before apply on the flushing process to evaluate the contamination background. The result indicating that the removal efficiency increased significantly to 88% for the homogeneous contamination condition with 50% of ethanol adding at 2 Pore Volume. Furthermore, 1, 2-dichloroethane and heavy metal concentrations in the contaminated soil are decreased significantly and lower than the regulated standard. The overview of removal efficiency from various mixture composition ratios can be arranged from high to low as follow: 50:50 of compost tea and ethanol mixture > 80:20 of compost tea and ethanol mixture > 100% compost tea > tap water.
According to above mention results, it indicate clearly that compost tea is able to treat 1, 2-dichloroethane compound with its high potential capability. In addition, the ethanol adding in the flushing mixture show a strongly increasing potential on removal process. Therefore, the soil treatment by compost tea are not only the environmental friendly method but also play role as a soil conditioner and the microbial nutrient source. For the future studies by this treatment method, the efficiency or purity of ethanol in compost tea should be considered to improve. Finally, to develop the successful of green remediation in carbon reduction procedure, the compost tea supposed to be the upper priority choice on competitiveness and demand in the biological treatment field.

目錄
摘要 摘要1
ABSTRACT 摘要3
誌謝
目錄 I
圖目錄 IV
表目錄 VI
第一章 前言 1
1.1 研究源起與動機 1
1.2 研究目的 3
第二章 含氯有機污染場址整治技術規範彙整 4
2.1 含氯有機化合物特性及危害 4
2.2 EDC於土壤與地下水中之管制規範 8
2.3 美國超級基金含氯有機化合物整治技術 10
2.4 國內外處理含氯有機物污染之研究 13
2.4.1 地下水污染整治技術 14
2.4.2 土壤污染整治技術 17
2.4.3 土壤沖洗法 22
2.4.4 生物整治 23
2.5 堆肥化/液肥整治技術 27
2.6 液肥之界面活性劑處理含氯有機物之污染 30
第三章 研究方法 33
3.1 執行架構 33
3.2 材料與設備 35
3.2.1 材料、試劑及藥品 35
3.2.2 液肥的製作 37
3.2.3 試驗設備 39
3.3 管柱試驗方法 41
3.3.1 模擬土壤基本性質分析 41
3.3.2 模擬EDC污染土壤配置方法 44
3.3.3 液肥處理EDC之管柱試驗 47
3.4 處理成效確認及品保品管措施 51
3.4.1 處理前後土壤毒害特性確認流程 51
3.4.2 水中VOCs之檢測方法及品保品管措施 52
3.4.3 土壤VOCs之檢測方法及品保品管措施 54
3.4.4 SVOCs之檢測方法及品保品管措施 56
3.4.5 廢棄物及底泥中金屬之檢測方法及品保品管措施 58
3.4.6 固體樣品中總汞之檢測方法及品保品管措施 59
3.4.7 碳氮比之檢測方法及品保品管措施 61
第四章 結果與討論 62
4.1 選用之土壤與液肥無害性確認 62
4.1.1 選用土壤之初始條件 62
4.1.2 選用之液肥初始條件 64
4.2 EDC之管柱沖排效率試驗 66
4.2.1 排出水EDC濃度之探討 66
4.2.2 沖排後土壤內EDC濃度之探討 73
4.2.3 質量平衡之探討 75
4.3 沖排前後土壤性質之變化 78
4.3.1 沖排前後SVOCs之變化 78
4.3.2 沖排前後重金屬之變化 80
4.3.3 沖排後之土壤肥力 82
第五章 結果與建議 83
5.1 結論……. 83
5.2 建議後續研究之課題 85
參考文獻 86
附件 92
附件一、土壤粒徑分析數據
附件二、固、液體VOCS可測得之60種化合物
附件三、固體SVOCS可測得之111種化合物


圖目錄
圖2-4.1 現地土壤沖洗系統 23
圖2-4.2 採滲水渠道之現地地下水生物整治法示意圖 24
圖2-4.3 採注入井之現地地下水生物整治法示意圖 24
圖2-4.4 典型現地地下水生物整治法（注入井）示意圖 26
圖2-6.1 污染土壤藉由堆肥法或堆肥的生物整治主要策略和機制 32
圖3-1.1 研究流程圖 34
圖3-3.1 土壤質地分類三角圖 42
圖3-3.2 管柱模擬試驗裝置圖 44
圖3-3.3 模擬均勻污染 44
圖3-3.4 模擬高濃度點源污染 44
圖3-3.5 過篩後細微粒土壤填充至管柱內 45
圖3-3.6 定流量將EDC注入管柱內 45
圖3-3.7 EDC注入後之靜置示意圖 46
圖3-3.8 土壤沖排及滲濾的模擬裝置圖 47
圖3-3.9 模擬均勻污染之管柱沖排過程情況 48
圖3-3.10 污染土樣取樣示意圖 48
圖3-3.11 模擬高濃度點源污染之管柱沖排過程情況 49
圖3-4.1 處理前後土壤毒害特性確認流程圖 51
圖4-2.1 不同沖排液於均勻污染之去除效率比較 67
圖4-2.2 不同沖排液於高濃度點源污染之去除效率比較（1~15 PV） 70
圖4-2.3 不同沖排液於高濃度點源污染之去除效率比較（1~55 PV） 70
圖4-3.1 均勻污染沖排前後重金屬變化之比較 80
圖4-3.2 高濃度點源污染沖排後重金屬變化之比較 81

 
表目錄
表2-1.1 1, 2-二氯乙烷之物理化學基本特性 6
表2-2.1 土壤含氯有機物污染之管制標準（土壤及地下水整治法） 8
表2-2.2 地下水中含氯有機物之管制標準（土壤及地下水整治法） 9
表2-3.1 美國超級基金DNAPL污染場址主要整治技術選用情形 10
表2-3.2 DNAPL整治技術之篩選矩陣 11
表2-3.3 DNAPL整治技術篩選矩陣之評估結果代號定義 12
表2-4.1 土壤及地下水污染整治技術 13
表2-4.2 污染物的整治技術 17
表3-2.1 試劑及標準品 36
表3-2.2 液肥中之生物界面活性物質 38
表3-2.3 分析儀器設備 39
表3-2.4 前處理設備 39
表3-2.5 其它設備 40
表3-3.1 模擬土壤之基本性質 43
表3-4.1 BFB校正需求 53
表3-4.2 氣相層析儀（GC）升溫之參數設定 56
表3-4.3 質譜儀（MSD）之參數設定 56
表4-1.1 選用土壤之初始條件 63
表4-1.2 液肥之初始條件 65
表4-2.1 不同沖排液於均勻污染之去除效率比較 68
表4-2.2 不同沖排液於高濃度點源污染之去除效率比較 71
表4-2.2 不同沖排液於高濃度點源污染之去除效率比較（續1） 72
表4-2.3 利用不同配方沖排均勻污染土壤試驗去除效率之比較 73
表4-2.4 利用不同配方沖排高濃度點源污染土壤試驗濃度之比較 74
表4-2.5 均勻污染試驗質量平衡分析表 75
表4-2.6 高濃度點源污染試驗質量平衡分析表 77
表4-3.1 均勻污染沖排前後SVOCs之變化 78
表4-3.2 高濃度點源污染沖排後SVOCs之變化 79
表4-3.3 均勻污染沖排前後重金屬之變化 80
表4-3.4 高濃度點源污染沖排後重金屬之變化 81
表4-3.5 不同沖排液沖排後土壤肥力之比較 82

Adani, Fabrizio, et al. "Surfactant Properties and Tetrachloroethene (PCE) Solubilisation Ability of Humic Acid-Like Substances Extracted from Maize Plant and from Organic Wastes: A Comparative Study." Chemosphere 78.8 (2010): 1017-22.
Atkinson, Roger. "Atmospheric Chemistry of VOCs and NO x." Atmospheric Environment 34.12 (2000): 2063-101.
Beffa, Trello, Michel Blanc, and Michel Aragno. "Obligately and Facultatively Autotrophic, Sulfur-and Hydrogen-Oxidizing Thermophilic Bacteria Isolated from Hot Composts." Archives of Microbiology 165.1 (1996): 34-40
Chen, Ming, et al. "Bioremediation of Soils Contaminated with Polycyclic Aromatic Hydrocarbons, Petroleum, Pesticides, Chlorophenols and Heavy Metals by Composting: Applications, Microbes and Future Research Needs." Biotechnology Advances (2015).
Cheung, Pui-Yi, and Brian K. Kinkle. "Effects of Nutrients and Surfactants on Pyrene Mineralization and Mycobacterium Spp. Populations in Contaminated Soil." Soil Biology and Biochemistry 37.7 (2005): 1401-5.
Childs, Jeffrey D., et al. "Improving the Extraction of Tetrachloroethylene from Soil Columns using Surfactant Gradient Systems." Journal of contaminant hydrology 71.1–4 (2004): 27-45. Print.
Chiou, Cary T., et al. "A Comparison of Water Solubility Enhancements of Organic Solutes by Aquatic Humic Materials and Commercial Humic Acids." Environmental science & technology 21.12 (1987): 1231-4. Print.
Chiou, Cary T., Daniel E. Kile, and Ronald L. Malcolm. "Sorption of Vapors of some Organic Liquids on Soil Humic Acid and its Relation to Partitioning of Organic Compounds in Soil Organic Matter." Environmental science & technology 22.3 (1988): 298-303.
Chiou, Cary T., and Daniel E. Kile. "Effects of Polar and Nonpolar Groups on the Solubility of Organic Compounds in Soil Organic Matter." Environmental science & technology 28.6 (1994): 1139-44.
Conte, Pellegrino, et al. "Soil Remediation: Humic Acids as Natural Surfactants in the Washings of Highly Contaminated Soils." Environmental Pollution 135.3 (2005): 515-22.
Daniele Daffonchio. "A Novel Reductive Dehalogenase, Identified in a Contaminated Groundwater Enrichment Culture and in Desulfitobacterium Dichloroeliminans Strain DCA1, is Linked to Dehalogenation of 1,2-Dichloroethane." 73.9 (2007): 2990–2999.
Diane S. Root, P. G. "In situ flushing.", (1997).
Fan, Chihhao, Minzhe Tsai, and Lo Tsui. "Structural Characterization of Bagasse-Derived Composts with Different Maturities and their Solubility Enhancing Effect on PCE and Toluene." Chemosphere 105 (2014): 95-9.
Fernández Rodríguez, M. D., et al. "Soil Pollution Remediation." Encyclopedia of Toxicology (Third Edition). Ed. Philip Wexler. Oxford: Academic Press, 2014. 344-355.
Fox, Catherine A. "PCB Biodegradation in Sediments. MR Harkness Et Al., 1993.“In Situ Stimulation of Aerobic PCB Biodegradation in Hudson River Sediments,” Science, Vol. 259, Pp. 503–8." Remediation Journal 3.3 (1993): 383-.
Gan, S., E. V. Lau, and H. K. Ng. "Remediation of Soils Contaminated with Polycyclic Aromatic Hydrocarbons (PAHs)." Journal of hazardous materials 172.2–3 (2009): 532-49.
Giorgia Quadri, Xiaosong Chen, James W Jawitz, Fulvia Tambone, Pierluigi Genevini, Franco Faoro, Fabrizio Adani. "Biobased Surfactant-Like Molecules from Organic Wastes: The Effect of Waste Composition and Composting Process on Surfactant Properties and on the Ability to Solubilize Tetrachloroethene (PCE)." 42.7 (2008): 2618-23.
Johnson, William P., and W. Wynn John. "PCE Solubilization and Mobilization by Commercial Humic Acid." Journal of contaminant hydrology 35.4 (1999): 343-62.
Ke, Lin, et al. "Effects of Humic Acid on Solubility and Biodegradation of Polycyclic Aromatic Hydrocarbons in Liquid Media and Mangrove Sediment Slurries." Chemosphere 76.8 (2009): 1102-8.
Kostiainen, Risto. "Volatile Organic Compounds in the Indoor Air of Normal and Sick Houses." Atmospheric Environment 29.6 (1995): 693-702.
Kuráň, P., and L. Soják. "Environmental Analysis of Volatile Organic Compounds in Water and Sediment by Gas Chromatography." Journal of Chromatography A 733.1–2 (1996): 119-41.
Langwaldt, J. H., and J. A. Puhakka. "On-Site Biological Remediation of Contaminated Groundwater: A Review." Environmental Pollution 107.2 (2000): 187-97.
Lee, Jiunn-Fwu, et al. "The Effect of Surfactants on the Distribution of Organic Compounds in the Soil solid/water System." Journal of hazardous materials 114.1–3 (2004): 123-30.
Lee, Minhee, Hyunmin Kang, and Wonhong Do. "Application of Nonionic Surfactant-Enhanced in Situ Flushing to a Diesel Contaminated Site." Water research 39.1 (2005): 139-46.
Li, Zhaohui. "Surfactant-Enhanced Oxidation of Trichloroethylene by permanganate––proof of Concept." Chemosphere 54.3 (2004): 419-23.
Liang, Qi, et al. "Application of Sewage Sludge and Intermittent Aeration Strategy to the Bioremediation of DDT- and HCH-Contaminated Soil." Journal of Environmental Sciences 26.8 (2014): 1673-80.
Liesbet Van Cauwenberght. "Electrokinetics.", (1997).
Mackay, D. M., et al. "A Controlled Field Evaluation of Continuous Vs. Pulsed Pump-and-Treat Remediation of a VOC-Contaminated Aquifer: Site Characterization, Experimental Setup, and Overview of Results." Journal of contaminant hydrology 41.1–2 (2000): 81-131.
McCarty, Perry L., Min-Ying Chu, and Peter K. Kitanidis. "Electron Donor and pH Relationships for Biologically Enhanced Dissolution of Chlorinated Solvent DNAPL in Groundwater." European Journal of Soil Biology 43.5–6 (2007): 276-82.
Mulligan, Catherine N. "Environmental Applications for Biosurfactants." Environmental Pollution 133.2 (2005): 183-98.
Naidu, Yuvarani, Sariah Meon, and Yasmeen Siddiqui. "Foliar Application of Microbial-Enriched Compost Tea Enhances Growth, Yield and Quality of Muskmelon (Cucumis Melo L.) Cultivated Under Fertigation System." Scientia Horticulturae 159 (2013): 33-40.
Park, Sung-Kil, and Angela R. Bielefeldt. "Non-Ionic Surfactant Flushing of Pentachlorophenol from NAPL-Contaminated Soil." Water research 39.7 (2005): 1388-96.
Quadri, Giorgia, et al. "Biobased Surfactant-Like Molecules from Organic Wastes: The Effect of Waste Composition and Composting Process on Surfactant Properties and on the Ability to Solubilize Tetrachloroethene (PCE)." Environmental science & technology 42.7 (2008): 2618-23.
Sabatini, David A., et al. "Integrated Design of Surfactant Enhanced DNAPL Remediation: Efficient Supersolubilization and Gradient Systems." Journal of contaminant hydrology 45.1–2 (2000): 99-121.
Siebielska, Izabela, and Robert Sidełko. "Polychlorinated Biphenyl Concentration Changes in Sewage Sludge and Organic Municipal Waste Mixtures during Composting and Anaerobic Digestion." Chemosphere 126 (2015): 88-95.
Situ, In. "Protocol for Bioremediation of Chlorinated Solvents using Edible Oil.", (2007).
Tsui, Lo, et al. "Reductive Dechlorination of Tetrachloroethene by Two Compost Samples with Different Maturity." Bioresource technology 102.22 (2011): 10498-504.
United States Department of Agriculture. "Soil Quality Test Kit Guide.", (1999).
Soil Survey Manual., (1993).
Vergieva T, Ilieva P, Popov T, Panev T. "Aromatic Hydrocarbons as Reproductive Hazards for Women in a Control Laboratory of Petrochemical Plant." 71, (1998).
Xu, Baizhuang, Paula Rantakallio, and Marjo-Riitta Jãrvelin. "Mortality and Hospitalizations of 24-Year-Old Members of the Low-Birthweight Cohort in Northern Finland." Epidemiology 9.6 (1998): 662-5.
何崇孝、林啟燦，「利用廚餘堆肥化程序處理1, 2-二氯乙烷污染土壤之研究」，碩士論文，國立高雄海洋科技大學，2013。
崔砢、陳秋楊、范致豪、連奕雯、林鳳祥、張榮恩、蔡旻哲，「利用堆肥液以提高生物溶解與降解四氯乙烯之研究」，EPA-99-GA103-03-A236-8，行政院環境保護署，2011。
曾瀚緯，「模擬受二氯乙烯污染之地下水結合厭氧脫氯與好氧共代謝之生物復育研究」，碩士論文，國立中興大學環境工程學系，2013。
王一雄，「土壤環境污染與農藥」，國立編譯館印行，1995。
盧至人，「地下水的污染整治」，國立編譯館，1997。
范勝洹、林啟燦，「應用植物營養液於土壤清洗法處理受柴油污染之土壤」，碩士論文，國立高雄海洋科技大學，2014。
蔡在唐、高志明、梁書豪、葉琮裕、黃文彥，「以生物可分解之界面活性劑沖洗法整治受dnapl污染之地下水」，界面科學會誌，P111-126，2007。
蔡在唐、高志明、葉琮裕、陳明華，「利用整治列車系統處理含氯有機物污染之地下水」，台灣土壤及地下水環境保護協會簡訊，P3-15，2008。
蔡文田、謝國鎔、張元銘，「表面清洗處理業使用含氯揮發性有機溶劑之安全衛生及空氣污染防治評估」，環保資訊月刊，64，2003。
蔡昀達，「地下水生物整治技術及案例介紹」，中興工程顧問股份有限公司，2001。
行政院環境保護署毒管處，毒理資料庫查詢，2015。
行政院環境保護署環署，土壤污染管制標準，2011。
行政院環境保護署，行政院環境保護署篩選認定毒性化學物質作業原則，2010。
陳呈芳，「重質非水相液體(Dnapl)污染調查技術介紹」，中興工程顧問股份有限公司，2007。
陳谷汎、高志明，「土壤及地下水物理/化學復育技術」，台灣土壤及地下水環境保護協會簡訊，第5期，P3-5，2002。
陳谷汎，「以生物復育法整治2,4-二氯酚污染之地下水」，碩士論文，國立中山大學環境工程研究所，2001。
韓吟龍，「地下水中三氯乙烯生物處理技術漫談」，桃園縣大學校院產業環保技術服務團環保簡訊，第六期，2010。
高志明、葉琮裕、蔡在唐、梁書豪、黃文彥，「應用整合型復育技術處理受燃料油污染之土壤及地下水」，EPA-94-U1U1-04-010，2005。
黃瑞彰、江汶錦，「有機液肥製作與應用」，臺南區農業改良場技術專刊，158，2014。
黃瓊儀，「界面活性劑與共同溶劑沖洗法對重非水相液體污染土壤移除效率之評估」，碩士論文，高雄師範大學，2013。