臺灣博碩士論文加值系統

含氯的芳香族有機化合物在環境中是非常毒之有機化合物，而且是屬於對人類致癌物之一。五氯酚Pentachlorophenol (PCP)是疏水性離子性有機化合物，通常在多種工業中被當作製造原料來使用。儘管五氯酚已被政府明令禁止使用多年，但台灣南部仍有大面積的五氯酚污染場址。化學氧化方法已被提出是可作為復育五氯酚現地污染場址方法之一，利用微奈米尺寸片錳礦(δ-MnO2)，其為錳氧化物之一，也是天然存在於土壤環境中的礦物質之一。爲了模擬五氯酚污染場址中，土壤底層處於厭氧和無光照系統下，利用一種自行設計之氣體釋放與吸收反應瓶，在無光照條件下，研究有氧或無氧(通氮氣除氧)狀態下，添加δ-MnO2對五氯酚進行氧化礦化脫羧作用和脫氯作用釋放出Cl–。
研究結果顯示，在有氧、無光照與無微生物活動條件下，添加δ-MnO2可促進五氯酚進行氧化礦化脫羧作用和脫氯作用釋放出Cl–。然而，在無氧(通氮氣除氧)狀態下，添加δ-MnO2對五氯酚進行的氧化礦化脫羧作用則明顯減少，而脫氯作用釋放出Cl–則成為主要反應。這明確指出添加δ-MnO2可對五氯酚進行非生物性破壞芳香苯環而釋放CO2 和Cl–。進而，計算釋放出的CO2和Cl–的莫耳比例，來推測不同反應系統下的反應機制。由於模擬近似污染場址的條件，在實驗室所獲得之參數和數據，對於規劃五氯酚現地污染整治過程是非常有用的，特別是可作為土壤底層包含地下水飽和層中，對五氯酚去毒作用的指導方針。

Chlorine–containing aromatic organic compounds are very toxic organic compounds in the environments and regarded as one of human carcinogens. Pentachlorophenol (PCP) is hydrophobic ionizable organic compound (HIOC) and is commonly used as manufacturing material in many industries. There is a large area of PCP contaminated site in southern part of Taiwan though PCP has been prohibited to use by the government authority for many years. Model chemical oxidation method has thus been proposed to remediate the PCP contaminated site in situ using micro-nano size δ-MnO2, which is one of manganese oxides and naturally occurring mineral in soil and associated environments. In order to simulate the anaerobic and dark situation of deep soil layers in PCP contaminated site, one kind of self-designed gas absorption and release reaction flask has been used to investigate the oxidative decarboxylation as well as mineralization and dechlorination to release Cl– of PCP enhanced by δ-MnO2 under air or N2 atmosphere and dark condition.
The results showed that δ-MnO2 enhanced the oxidative decarboxylation as well as mineralization and dechlorination to release Cl– of PCP under air and dark in the absence of microbial activity. However, under N2 atmosphere oxidative decarboxylation as well as mineralization of PCP was drastically reduced but dechlorination to release Cl– of PCP became the dominant reaction. This clearly indicates abiotic ring cleavage of aromatic ring of PCP to release CO2 and Cl– enhanced by δ-MnO2. Further, calculated mole ratios of released CO2 to Cl– were thus used to sketch the reaction mechanisms of different reaction systems. Due to similar simulated condition in laboratory to that in contaminated site, the parameters and respective data obtained thus have highly potential to be used as a guideline for planning the remediation process of PCP contaminated site in situ and especially for the detoxification of PCP in deeper soil profile including groundwater saturated layer.

目 錄
中文摘要I
AbstractII
誌謝IV
目 錄V
表 目 錄VII
圖 目 錄VIII
第一章 前 言1
第二章 前人研究3
第三章 材料與方法20
3.1 試驗材料20
3.2 試驗方法28
3.3 儀器分析32
第四章 結果與討論39
4.1 供試土壤基本性質39
4.2 δ-MnO2尺寸鑑定40
4.3 供試污染土壤回收率42
4.4 安定性試驗43
4.5 有、無添加δ-MnO2在不同時間下對不同污染土壤之礦化效率44
4.6 有、無氧氣對添加δ-MnO2於不同污染土壤之作用機制61
4.7 有、無氧氣在不同時間下對添加δ-MnO2於不同污染土壤之化學計量74
4.8 微生物之生長情形76
第五章 結 論77
參考文獻78
附 錄83
表 目 錄
表2-1 PCP物理化學特性4
表3-1 試驗藥品與材料20
表3-2 試驗設備與儀器21
表3-3 IC分析條件35
表3-4 HPLC分析條件 36
表4-1 供試土壤基本性質39
圖 目 錄
圖2-1 五氯酚在環境中的宿命6
圖2-2 五氯酚之光解反應途徑8
圖2-3 五氯酚製程中戴奧辛產生機制10
圖2-4 二氧化錳之表面構造及反應途徑15
圖2-5 不同合成的錳氧化物之間的關係圖17
圖3-1 δ-MnO2製備流程圖25
圖3-2 實驗流程圖29
圖3-3 氣體吸收釋放反應瓶30
圖3-4 碳酸鹽系統在不同pH條件下的分佈圖33
圖3-5 IC層析效能圖譜34
圖3-6 PCP之檢量線37
圖3-7 PCP之滯留時間38
圖4-1 場發射掃描式電子顯微鏡(FE-SEM)，分析鑑定δ-MnO2尺寸(放大10,000倍)40
圖4-2 場發射掃描式電子顯微鏡(FE-SEM)，分析鑑定δ-MnO2尺寸(放大100,000倍)41
圖4-3 高效能粒徑分析儀(HPPS)，分析鑑定δ-MnO2粒徑41
圖4-4 供試污染土壤之回收率42
圖4-5 供試污染土壤之年降解率43
圖4-6 有、無添加δ-MnO2在不同時間下對污染石英砂之CO2釋放45
圖4-7 有、無添加δ-MnO2在不同時間下對污染石英砂之Cl-釋放46
圖4-8 有、無添加δ-MnO2在不同時間下對污染石英砂之礦化降解率48
圖4-9 有、無添加δ-MnO2在不同時間下對污染紅壤之CO2釋放49
圖4-10 有、無添加δ-MnO2在不同時間下對污染紅壤之Cl-釋放50
圖4-11 有、無添加δ-MnO2在不同時間下對污染紅壤之礦化降解率52
圖4-12 有、無添加δ-MnO2在不同時間下對污染沖積土之CO2釋放53
圖4-13 有、無添加δ-MnO2在不同時間下對污染沖積土之Cl-釋放54
圖4-14 有、無添加δ-MnO2在不同時間下對污染沖積土之礦化降解率56
圖4-15 有、無添加δ-MnO2在不同時間下對不同污染土壤之CO2釋放57
圖4-16 有、無添加δ-MnO2在不同時間下對不同污染土壤之Cl-釋放58
圖4-17 有、無添加δ-MnO2在不同時間下對不同污染土壤之礦化降解率60
圖4-18 有、無氧氣在不同時間下對添加δ-MnO2於污染石英砂之CO2釋放62
圖4-19 有、無氧氣在不同時間下對添加δ-MnO2於污染石英砂之Cl-釋放63
圖4-20 有、無氧氣在不同時間下對添加δ-MnO2於污染石英砂之礦化降解率65
圖4-21 有、無氧氣在不同時間下對添加δ-MnO2於污染紅壤中之CO2釋放66
圖4-22 有、無氧氣在不同時間下對添加δ-MnO2於污染紅壤中之Cl-釋放67
圖4-23 有、無氧氣在不同時間下對添加δ-MnO2於污染紅壤中之礦化降解率69
圖4-24 有、無氧氣在不同時間下對添加δ-MnO2於污染沖積土中之CO2釋放70
圖4-25 有、無氧氣在不同時間下對添加δ-MnO2於污染沖積土中之Cl-釋放71
圖4-26 有、無氧氣在不同時間下對添加δ-MnO2於污染沖積土中之礦化降解率73
圖4-27 有、無氧氣在不同時間下對添加δ-MnO2於污染石英砂之化學計量關係74
圖4-28 有、無氧氣在不同時間下對添加δ-MnO2於污染紅壤之化學計量關係75
圖4-29 有、無氧氣在不同時間下對添加δ-MnO2於污染沖積土之化學計量關係76

行政院環境保護署，土壤酸鹼值測定法，NIEA S410.62C。
行政院環境保護署，土壤中陽離子交換容量-醋酸鈉法，NIEA S202.60A。
王一雄，土壤環境污染與農藥，明文書局，台北，第1-648頁(1997)。
王守範，「五氯酚鈉處理木材浸水後藥劑流失性之研究」，台灣省林業試驗所報告，第一六六號(1968)。
王傳新，「作物需肥診斷技術-鮑氏土壤機械法」，台灣省農試所特刊，第十三期，第27-29頁(1981)。
宋德高，「台灣地區環境中含氯毒性有機化合物分析研究」，博士論文，國立清華大學，新竹(1995)。
袁紹英、張碧芬，「土壤受多環芳香族碳氫化合物污染之生物整治」，第六屆土壤污染防治研討會論文集，第19-36頁(1999)。
曾國輝，化學(上、下)，藝軒圖書出版社(2001)。
陳琪婷、黃春蘭、楊磊、蔡明惠，「以二氧化錳氧化降解水中污染物之研究」，中華民國環境工程學會第二十八屆廢水處理技術研討會論文集，台中(2003)。
黃昆德、黃文彥、高志明、林明勳，「高錳酸鉀氧化法處理三氯乙烯污染地下水之反應機制探討及去瓶頸反應研究」，中華民國環境工程學會第二屆土壤與地下水研討會論文集，台南(2004)。
陳嘉慶，「土壤pH與有機組成分對芘溶出影響之研究」，碩士論文，朝陽科技大學，台中(2007)。
李起睿，「pH值與有機質對五氯酚於土壤中吸附與脫附之影響」，碩士論文，朝陽科技大學，台中(2007)。
張志豪，「奈米級δ-MnO2與TiO2對芘污染土壤之催化轉化作用」，碩士論文，朝陽科技大學，台中(2007)。
Chiou, C. T., Proter, P. E., and Schemdding, D. W., “Partition Equilibria of Nonic Organic Matter and Water,” Environ. Sci. Technol., Vol. 17, No. 4, pp.227-231(1983).
Cleasby, J. L., ”Iron and manganese removal-a case study,” J. Am. Wat. Wks. Ass., 67(2):147-149(1975).
Crosby, D. G., “Environmental chemistry of pentachlorophenol,” Pure and Appl. Chem., Vol. 53(5):1051-1080(1981).
Driehaus, W., Seith, R., and Jekel, M., “Oxidation of arsenate(III) with manganese oxides in water treatment,” Wat. Res., 29(1):297-305(1995).
Fisher, B., “Pentachlorophenol: Toxicology and Environmental Fate,” Journal of Pesticide Reform, Vol. 11, No. 1, pp.2-5(1991).
Fukushima, M. and Tatsumi, K., “Degradation Pathways of Pentachlorophenol by Photo-Fenton Systems in the Presence of Iron（Ⅲ）, Humic Acid, and Hydrogen Peroxide,” Environ. Sci. Technol., Vol. 35, pp.1771-1778(2001).
Germida, J. J. and Casida, L. E. Jr., “Myceloid growth of Arthrobacter globiformis and other Arthrobacter species,” J. Bacteriol. 144:1152-1158(1980).
Ghosh, U., Talley, J. W., and Luthy, R. G., “Particle-scale investigation of PAH desorption kinetics and thermodynamics from sediment,” Environ. Sci. Technol., Vol. 35, pp.3468-3475(2001).
Gustafsson, O., Haghseta, F., Chan, C., Macfarlane, J., and Gschwend, P. M., “Quantification of the dilute sedimentary soot phase : implications for PAH speciation and bioavailability,” Environ. Sci. Technol, Vol. 31, pp.203-209(1997).
Hurst, C. J., Sorensen, D. L., Sims, R. C., Mclean, J. E., Sims, J. L., and Huling, S., “Soil gas oxygen tension and pentachlorophenol biodegradation,” Journal of Environmental Engineering, 123(4):364-370(1997).
Jokic, A., Wang, M. C., Liu, C., Frenkel, A. I., and Huang, P. M., “Integration of the polyphenol and Maillard reactions into a unified abiotic pathway for humification in nature: the role of δ-MnO2,” Organic Geochem. 35:747-762(2004).
Knocke, W. R., Hoehn, R. C., and Sinsabangh, R. L., “Using alternative oxidants to remove dissolved manganese from waters laden with organics,” J. Am. Wat. Wks. Ass., 79(3):75-79(1987).
Lamparski, L. L., Stehl, R. H., and Johnson, R. L.,”Photolysis of pentachlorophenol-treated wood. Chlorinated dibenzo-p-dioxin formation,” Environ. Sci. Technol., 14(2), pp.196–200(1980).
Manickam, M., Singh, P., Issa, T. B., Thurgate, S., and Marco, R. D., “Lithium Insertion into Manganese Dioxide Electrode in MnO2/Zn Aqueous Battery,” Journal of Power Sources, 130:254-259(2004).
McKenzie, R. M., “The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese,” Mineral Magazine, 38:493-502(1971).
Morgan, J. J. and Stumm, W., “Colloid-chemical properties of manganese dioxide,” J. Colloid Sci., 19:347-359(1964).
Olson, B. M., McKercher, R. B., and Germida, J. J., “Microbial population in trifluralin-treated soil,” Plant Soil, 76:379-387(1984).
Pandiyan, T., Rivas, O. M., Martinez, J. O., Amezcua, G. B., and Martinez-Carrillo, M. A., “Comparison of Methods for the Photochemical Degradation of Chlorophenols,” Journal of Photochemistry and Photobiology A: Chemistry, Vol. 146, pp.149-155(2002).
Pecchi, G., Reyes, P., Sanhueza, P., and Villasenor, J., “Photocatalytic degradation of pentachlorophenol on TiO2 sol-gel catalysts,” Chemosphere, Vol. 43, pp.141-146(2001).
Poerschmann, J. and Kopinke, R. D., “Sorptlon of Very Hydrophobic Organic Compounds(VHOCs) on Dissolved Humic Organic Matter(DOM). 2.Measurement of Sorption and Application of a Flory-Huggins Concept T oInterpret the Data,” Environ. Sci. Technol., Vol. 35, pp.1142-1148(2001).
Posselt, H. S. and Anderson, F. J., “Cation sorptopnon colloidal hydrous manganese dioxide,” Environ. Sci. Technol., 2(12):1087-1093(1968).
Rhoades, J. D., “Soluble salts, Methods of soil analysis (Page, A. L., Miller, R. H., and Keeney, D. R. eds.), Part2. 2nd ed, Agronomy Monogrphy 9, ASA and SSSA.,” Madision, Wisconsin, pp.167-179(1982).
Tiessen, H., Bettany, J. R., and Stewart, J. W. B., “An improved method for the determination of carbon in soils and soil extracts by dry combustion,” Commun. Soil Sci. Plant Anal., Vol. 12, pp.211-218(1981).
Tamer, E., Hamid, Z., Aly, A. M., Ossama, E. T., Bo, N., and Benoit, G., “Sequential UV-biological degradation of chlorophenols,” Chemosphere, Vol. 63, pp.277-284(2006).
Van Noort, P. C. M., Jonker, M. T. O., and Koelmans. A. A., “Modeling maximum adsorption capacities of soot and soot-like materials for PAHs and PCBs,” Environ. Sci. Technol., Vol. 38, pp.3305-3309(2004).
Wang, M. C., “Catalysis of nontronite in phenols and glycine transformations,” Clay Clay Miner., Vol. 39(2):202-210(1991).
Wang, M. C. and Huang, P. M., “Significance of Mn(IV) oxide in the abiotic ring cleavage of pyrogallol in natural environments,” Sci. Total Environ., 113:147-157(1992).
Wang, M. C. and Huang, P. M., “Cleavage of 14C-labelled glycine and its polycondensation withpyrogallol as catalyzed by birnessite,” Geoderma 124:415-426(2005).
Wang, T. S. C., S. W. Li, and Huang, P. M., “Catalytic Polymerization of Phenolic Compounds by a Latosol,” Soil Sci., Vol. 126, pp.81-86(1978).
Wang, Y. J., Lee, C. C., Chang, W. C., Liou, H. B., and Ho, Y. S., “Oxidative stress and liver toxicity in rats and human hepatoma cell line induced by pentachlorophenol and its major metabolite tetrachlorohydroquinone,” Toxic. Lett., Vol.122, pp.157-169(2001).
Wong, A. S. and Crosby, D. G., “Pentachlorophenol: Chemistry pharmacology and environmental toxicology,” Plenum, New York, pp.19-25(1978).