臺灣博碩士論文加值系統

熱處理方式通常能有效用於去除土壤中之戴奧辛，但對於大量或濃度較低之戴奧辛污染土壤，其整治成本過高。因此研發效果佳成本低的整治方法有其必要性。
本研究嘗試以低價格的大豆油作為萃取土壤中戴奧辛的溶劑，在實驗以土/油重量比1:1之條件下，萃取溫度分別設定為60°C、40°C和室溫，萃取時間設定為8小時和24小時，而萃取的次數為1次、3次和6次，每次皆更換乾淨的大豆油進行萃取，並將萃取後之土壤進行水洗三次和紫外線降解戴奧辛的成效測試，最後並研究大豆油淨化再使用的可行性，以降低處理成本。
研究結果顯示大豆油能將戴奧辛濃度高達79,100 ng I-TEQ/kg的原始土壤於室溫下經每次8小時重複3次萃取後，其濃度降至1,900 ng I-TEQ/kg，去除率可高達97％。然而若將萃取後之戴奧辛土壤進行水洗3次，再經紫外線或太陽光照射10天，可再降低土壤中戴奧辛約600~700 ng I-TEQ/kg。將萃取一次後之大豆油置於254nm及365nm紫外線燈管下經7天的照射後，所測得的戴奧辛含量不減反增，由文獻資料得知五氯酚會經由紫外線照射合成戴奧辛，而本研究使用之污染土壤中恰含有高濃度之五氯酚，故此萃取後之大豆油不適合使用紫外線照射法進行淨化。大豆油淨化再利用實驗中，以粉狀活性碳與萃取一次後之大豆油(約26,300ng I-TEQ/kg)於室溫下進行吸附反應4小時，可大幅降低大豆油中戴奧辛濃度至148 ng I-TEQ/kg，去除率達99％，淨化後之大豆油再次利用於萃取戴奧辛污染土壤，以室溫下每次8小時重複3次萃取後，土壤中戴奧辛濃度降為2,132 ng I-TEQ/kg，去除率可達93%。綜合上述實驗，證明大豆油可有效將存在於土壤中之戴奧辛萃取出來，達到土壤整治之目的。

Thermal treatment is usually effective in removing dioxins in the soil, but for large or low concentrations of dioxins contaminated soil, the remediation costs are too high. So the research and development of efficient and low cost of treatment method has its necessity.
This study attempts to use the most popular and low-cost soybean oil in Taiwan as the dioxin extraction solvent. Experimental conditions of soil/oil weight ratio of 1/1, extraction temperature was set to 60 °C, 40 °C and room temperature (25 °C). The extraction time was set to 8 hours and 24 hours, and repeated for 1 ,3and 6 times, each time adds a new soybean oil. After extraction, the soil was washed with water and using ultraviolet to degrade dioxin in the soil and the oil. Finally, the feasibility study of soybean oil regeneration was tested to reduce the remediation cost.
The results showed that the soybean oil was able to reduce the dioxin concentration of up to 79,100 ng I-TEQ/kg of raw soil at room temperature by repeating 3 times, each time for 8 hours, and the concentration was reduced to 1,900 ng I-TEQ/kg. The removal efficiency is 97%. When the extracted soil after been washed 3 times, and then degraded by ultraviolet light or sunlight for 10 days, the dioxin concentration can be further reduced by another 600 ~ 700 ng I-TEQ/kg.
After the extraction the soybean oil was exposed under 254nm and 365nm UV lamp for 7 days, the dioxin concentration increased. It is because that the contaminated soil used in the study contains a high concentration of pentachlorophenol, it was also extracted by oil and then synthesized by ultraviolet to form dioxin.
In the soybean oil purification and reuse experiment, the powdered activated carbon was mixed with the extracted soybean oil (about 26,300 ng I-TEQ / kg) at room temperature for 4 hours. It significantly reduced the dioxin concentration in the soybean oil to 148 ng I-TEQ / kg, the removal rate was 99%. After purification, the soybean oil was reused in the extraction of dioxin-contaminated soil, and the concentration of dioxins in the soil was reduced to 2,132 ng I- TEQ / kg, the removal rate of up to 93%. Based on the above experiments, it was proved that the soybean oil can effectively extract the dioxins which is present in the soil and achieve the purpose of soil remediation.

中文摘要 I
英文摘要 III
致謝 V
目錄 VI
圖目錄 VIII
表目錄 X
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 1
第二章 文獻回顧 3
2.1 戴奧辛物化性質 3
2.2 PCDD/Fs來源 5
2.3 PCDD/Fs對人體健康危害 9
2.4 戴奧辛污染案例 10
2.5 土壤污染整治技術 11
2.5.1生物降解法 11
2.5.2物理處理法 12
2.5.3活性碳吸附 15
2.5.4化學處理法 16
第三章 研究方法與材料 21
3.1實驗材料 21
3.1.1土壤樣品 21
3.1.2大豆油 21
3.1.3其他試藥 21
3.2實驗設備 21
3.3實驗內容 25
3.4實驗步驟 28
3.4.1土壤萃取實驗 28
3.4.2大豆油淨化實驗 28
3.4.3紫外線光解實驗 29
3.4.4再生油再萃取土壤實驗 29
第四章 結果討論 32
4.1原土壤戴奧辛濃度分析 32
4.1.1篩分分析 33
4.2大豆油萃取實驗 34
4.2.1 萃取參數探討 34
4.2.2溫度參數探討 38
4.2.3萃取時間探討 41
4.2.4不同混合/攪拌裝置去除效果比較 43
4.3大豆油淨化試驗 44
4.4紫外線光解實驗 49
4.4.1萃取戴奧辛之大豆油紫外光降解實驗 49
4.4.2水洗試驗 51
4.4.3水洗後土壤紫外光降解實驗 52
4.4.4不同紫外光降解試實驗 53
4.5再生之大豆油萃取試驗 53
4.6成本分析 54
第五章 結論 55
參考文獻 57

1.陳呈方，“戴奧辛污染土壤整治技術”，水利土木科技資訊第33期，PP 1-8，2006
2.Isosaari, P., Tuhkanen T. and Vartiainen T.,“Use of Olive Oil for Soil Extraction and Ultraviolet Degradation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans＂Environ Sci Technol, 35 (6), 1259-1265，2001
3.吳婉怡，“界面活性劑整治戴奧辛污染土壤之可行性研究”，國立中央大學環境工程研究所碩士論文，2013
4.McKay, G., “Dioxin characterization,formation and minimization during municipal solid waste(MSW) incineration: review”, Chemical Engineering Journal,Vol.86,No3,pp.343-368,2002
5.Ahlborg, U. G.,Brouwer,A., Fingerhut, M.A., Jacobson, J .L.,Jacobson,S. W., Kennedy, S.W., and van den Berg, M., “Impact of polychlorinated dibenzo-p-dioxin, dibenzofurans,and biphenyls on human and environmental health, with special emphasis on application of the toxic equivalency factor concept”European Journal of pharmacology,Vol.228,No.4,pp.179-199,1992
6.Van den Berg, M.,Birnbaum,L.S., Denison, M., Vito,M.D.,Farland,W.,Feeley,M.,Fiedler.,H.,Hakansson, H.,Hanberg,A.,Haws,L,Rose,M., Safe, S., Schrenk, D.,Tohyama, C., Tritscher, A., Tuomisto, J.,Tysklind, M., Walker, N. and Peterson, R.E.,“The 2005 World Health Organization re-evaluation of human and mammalian toxic equivalency factors for dioxins and dioxin-like compounds”,Toxicological Science,Vol.93,No2,pp.223-241,2006
7.Kulkarni, P. S.,Crespo, J., and Afonso, CAM “Dioxins sources and current remediation technologies – A review”Environment international, 34:139-153,2008
8.張書豪，“以活性碳吸附煙道排氣中戴奧辛之初步研究”，國立中央大學環境工程研究所碩士論文，2000
9.Aittola, J. P., Paasivirta, J. and Vartiainen, A. “Measurements of Oraganochloro Compounds at a Metal Reclamation Plant＂Chemosphere,Vol. 27,pp.65-72,1993.
10.Eduljee, G. H. ,Dyke, P. “An Updated Inventory of Potential PCDD and PCDF Emission Sources in the UK”The Science of the Total Environment,Vol.177,pp.303-321, 1996
11.Kulkarni, P. S.,Crespo, J., and Afonso, CAM “Dioxins sources and current remediation technologies – A review”Environment international, 34:139-153,2008
12.Fisher, B. “Pentachlorophenol:Toxicology and Environmental Fate.”Journal of Pesticide Reform, 11(1),2-500
13.鍾仁祺，“台灣地區農業土壤之戴奧辛研究”,環境檢驗所環境調查研究年報第9期，pp.41-48，2002
14.中石化/台全公司，“台南市安順廠區汞及五氯酚污染調查”，1999
15.行政院環保署“台南市中石化安順廠整治土壤及地下水污染範圍調查及整治工作建議計畫”，2004
16.Stellman, J.M., Stellman, S.D., Weber, T., Tomasallo, C., Stellman, A.B. and Christian, R. “A geographic information system for characterizing exposure to Agent Orange and other herbicides in Vietnam”, Environ. Health Perspect., Vol. 111, pp.321–328.,2003
17.Aoki, Y. “Polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans as endocrine disrupters – what we have learned from Yusho” disease, Environ. Res., Vol. 86, pp.2–11, 2001
18.Matsumura, F.and Benezet, H.J. “Studies on the bioaccumulation and microbial degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin”,Environmental Health Perspectives,Vol.5,pp.253-258.,1973
19.Hutzinger, O., Blumich, M.J., Vanderberg, M. and Olie, K., “Sources and fate of PCDDs and PCDFs-An overview”,Chemospere,Vol.14,pp.581-600,1985
20.吳裕民，“以植生復育技術處理受戴奧辛及汞污染土壤之研究”國立中山大學海洋環境工程學系博士論文，2013
21.Ishii, K.,Furuichi. T. and Masahiko. S., “Development of a bioreactor system for treatment of dioxins-contaminated soils and incinerated”, Organohalogen Compounds, Vol.66,pp.1257-1261,2004
22.Khodadoust A.P., Suidan M.T., Acheson C.M. and Brenner R. “Solvent extraction of pentachlorophenol from contaminated soils using water-ethanol mixtures” Chemosphere, 38, 2681-2693,1999
23.Paterson I.F., Chowdhry B.Z. and Leharne S.A. “ Polycyclic aromatic hydrocarbon extraction from a coal tar-contaminated soil using aqueous solutions of nonionic surfactants”Chemosphere, 38, 3095-3107,1999
24.Smyth T.J., Zytner R.G. and Stiver W.H. “Influence of water on the supercritical fluid extraction of naphthalene from soil.” Journal of Hazardous Materials, B67, 183-196.,1999
25.Hawthorne S.B. and Grabanski C.B.“Correlating selective supercritical fluid extraction with bioremediation behavior of pahs in a filed treatment plot.” Environ. Sci. Technol, 34(19), 4103-4110.,2000
26.Dadkhah A.A. and Akgerman A. “Hot water extraction with in situ wet oxidation: PAHs removal from soil.”Journal of Hazardous Materials, B93, 307-320.,2002
27.Gong Z., Alef K., Wilke B.M. and Li P. “Dissolution and removal of PAHs from a contaminated soil using sunflower oil” Chemosphere. 58, 291–298.,2005a
28.Gong Z., Alef K., Wilke B.M., Mai M. and Li P.“Assessment of microbial respiratory activity of a manufactured gas plant soil after remediation using sunflower oil”J Hazard Mater, 124, 217–223.,2005b
29.Gong, Z. Wilke B.M., Alef K. and Li P.“Influence of soil moisture on sunflower oil extraction of polycyclic aromatic hydrocarbons from a manufactured gas plant soil”Sci. Total Environ. 343, 51–59.,2005c
30.Isosaari P., Tuhkanen T. and Vartiainen T.,“Use of Olive Oil for Soil Extraction and Ultraviolet Degradation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans”Environ Sci Technol, 35 (6), 1259-1265.,2001
31.Bragato M. and El Seoud O.A.“ Formation, properties, and “ex situ” soil decontamination by vegetable oil-based microemulsions”Journal of Surfactants and Detergents, 6(2), 143-150.,2003
32.Pannu J.K., Singh A. and Ward O.P.“Vegetable oil as a contaminated soil remediation amendment: application of peanut oil for extraction of polycyclic aromatic hydrocarbons from soil”Process Biochemistry, 39(10), 1211-1216.,2004
33.Pannu J.k., Singh A. and Ward O.P.“Influence of peanut oil on microbial degradation of polycyclic aromatic hydrocarbons”Canadian Journal of Microbiology, 49, 508-513.,2003
34.孫翼飛、巩宗强、苏振成、王晓光、图影，應用表面活性劑-生物柴油微乳液去除污染土壤中多環芳香烴，環境工程學報，2012
35.Gong Z., Wilke B.M., Alef K., Li P. and Zhou Q.“Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments”Chemosphere. 62, 780–787.,2006
36.Proffitt C.E., Devlin D.J. and Lindsey M.“ Effects of oil on mangrove seedlings grow under different environmental conditions”Mar. Pollut. Bull, 30, 788-793.,1995
37.Dougherty E.J., Overcash M.R. and Carbonell R.G.“ Diffusivity of 2,3,7,8-tetrachlorodibenzo-p-dioxin in organic solvents”Hazard. Waste Hazard. Mater. 8, 43-53.,1991
38.Yap C.L., Gan S. and Ng H.K.“Application of vegetable oils in the treatment of polycyclic aromatic hydrocarbons-contaminated soils”Journal of Hazardous Materials, 177, 28-41.,2010
39.Podoll R.T., Irwin .C. and Parish H.J.“Dynamic studies of naphthalene sorption on soil from aqueous solution”Chemosphere, 18(11-12), 2299-2312.,1989
40.日本環境省，「平成18年度低コスト･低負荷型土壌汚染調査対策技術検討調査及びダイオキシン類汚染土壌浄化技術等確立調査」，2007
41.Bolsing, F., “In remediation engineerg of contaminated soil”, Mercel Dekker Inc.,2000
42.行政院環保署，同時處理土壤中戴奧辛、五氯酚及汞之整合性技術開發，2013
43.Wan J., Chai L., Lu X., Lin Y. and Zhang S.“Remediation of hexachlorobenzene contaminated soils by rhamnolipid enhanced soil washing coupled with activated carbon selective adsorption”Journal of Hazardous Materials, 189(1-2), 458-464.,2011
44.Kawashima A., Katayama A., Matsumoto N. and Honda K.“Physicochemical characteristics of carbonaceous adsorbent for dioxin-like polychlorinated biphenyl adsorption”Chemosphere 83, 823–830.,2011
45.Karademir A., Bakoglu M., Taspinar F. and Ayberk S“Removal of PCDD/Fs from flue gas by a fixed-bed activated carbon filter in a hazardous waste incinerator”Environ. Sci. Technol. 38, 1201–1207.,2004
46.Tseng H.H., Lu C.Y., Chang F.Y., Wey M.Y. and Cheng H.T.“Catalytic removal of NO and PAHs over AC-supported catalysts from incineration flue gas: bench- scale and pilot-plant tests”Chem. Eng. J. 169, 135–143.,2011
47.Xie, L.P.,“Production of activated carbon from municipal solid organic waste. In: Doctoral thesis, Institute of Procee Engineering”Chinese Academy of Sciences, Beijing.,2003
48.Graffar, A., Tabata, M., Mazher, F. and Mashiatullah, A.,“High dechlorination of PCBs catalysed by carbon under mild conditions”Environ. Chem. Lett. 10, 171– 176.,2012
49.Maes J., Meulenaer B.D., Heerswynghels P.V., Greyt W.D., Eppe G., Pauw E.D. and Huyghebaert A.“Removal of Dioxins and PCB from Fish Oil by Activated Carbon and Its Influence on the Nutritional Quality of the Oil”Journal of the American Oil Chemists Society, 82 (8), 593-597.,2005
50.Oterhals, A., Solvang, M., Nortvedt, R. and Berntssen, Marc H. G.“Optimization of activated carbon-based decontamination of fish oil by response surface methodology”European Journal of Lipid Science and Technology, 109, 691-705.,2007
51.Nakashima, T., Takamatsu, J., Inoue, M., Matsuike, T., Koyama, T. and Matsuo, T., “Remediation project report of dioxins contaminated soil in Nose Town, Osaka Japan” Organohalogen Compounds, Vol 69, pp. 869-872.,2007
52.Vogg, H. and Stieglitz, L., “Thermal behavior of PCDD/PCDF in fly ash from municipal incinerators” Chemosphere, Vol. 15, pp. 1373–1378 ,1986
53.Hagenmaier, H., Kraft, M., Brunner, H. and Haag, R., “Catalytic effects of fly ash from waste incineration facilities on the formation and decomposition of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans” Environmental Science & Technology, Vol. 21, pp. 1080-1084.,1987
54.Stieglitz, L. and Vogg, H., “On formation conditions of PCDD/PCDF in fly ash from municipal waste incinerators”Chemosphere, Vol. 16, pp. 1917-1922.,1987
55.Schetter, G., Horch, K., Stuetzle, R., Brunner, H. and Hagenmaier, H., “Low temperature thermal treatment of filter ash from municipal waste incinerators for dioxin decomposition on a technical scale” Organohalogen Compounds, Vol. 3, pp. 165-168.,1990
56.Takasuka, G., Itaya, M. and Kojima, S., “Thermal decomposition of PCDDs/PCDFs in MSW incineration fly ash” Organohalogen Compounds, Vol. 19, pp. 491-494.,1994
57.Collina, E., Lasagni, M. and Pitea, D., “Degradation of octachlorodibenzofuran and octachlorodibenzo-p-dioxin spiked on fly ash: kinetics and mechanism” Environmental Science & Technology, Vol. 29, pp. 577-585.,1995
58.Addink, R., Paulus, R., Olie, K., “Prevention of PCDD/F formation on municipal waste incinerator fly ash using nitrogen and sulfur compounds” Environmental Science & Technology, Vol. 30, pp. 2350-2354.,1996
59.Taniguchi, S., Hoaomi, M., Murakami, A., Iimura, S., Usukura, K. and Ozawa, S., “Chemical decomposition of toxic organic chlorine compounds” Chemosphere, Vol. 32, pp. 199-202.,1996
60.Addink, R., Olie, K., “Role of oxygen in formation of polychlorinated dibenzo-p-dioxins/dibenzofurans from carbon on fly ash”EnvironmentalScience & Technology, Vol. 29, pp. 1586-1590.,1995
61.Zhong Y., Overcash M.R. and Mcpeters A.L.“Photodrgradation of TCDD in soil containing organic solvents”Environmental Geochemistry and Health, 16, 235-240.,1993
62.Hilarides, R., Gray, K., Guzzetta, J., Cortellucci, N. and Sommer, C“ Radiolytic degradation of 2,3,7,8-TCDD in artificially contaminated soils”Environ. Sci. Technol. 28, 2249-2258.,1994
63.Isosaari P., Laine O., Tuhkanen T. and Vartiainen T.“Photolysis of polychlorinated dibenzo-p-dioxins and dibenzofurans dissolved in vegetable oils: influence of oil quality”Sci Total Environ, 340 (1-3), 1-11.,2005
64.Wagenaar W.J., Boelhouwers E.J., de Kok H.A.M., Groen C.P., Govers H.A.J., Olie K., de Gerlache J. and de Rooij C.G.“A comparative study of the photolytic degradation of octachlorodibenzofuran (OCDF) and octachlorobidenzo-p-dioxin” Chemosphere 31, 2983-2992.,1995
65.Dung M.H., O'Keefe P.W.“Comparative rates of photolysis of polychlorinated dibenzofurans in organic solvents and in aqueous solutions”Environ Sci Technol, 28(4), 549-54.,1994
66.Konstantinov A. and Bunce N.J“Photodechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran in alkane solvents in the absence and presence of triethylamine. J. Photochem. Photobiol. A”Chem. 94, 27-35.,1996
67.Wagenaar W.J., Boelhouwers E.J., de Kok H.A.M., Groen C.P., Govers H.A.J., Olie K., de Gerlache J. and de Rooij C.G.“A comparative study of the photolytic degradation of octachlorodibenzofuran (OCDF) and octachlorobidenzo-p-dioxin” Chemosphere 31, 2983-2992.,1995
68.Isosaari P., Tuhkanen T. and Vartiainen T.,“Use of Olive Oil for Soil Extraction and Ultraviolet Degradation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans”Environ Sci Technol, 35 (6), 1259-1265.,2001
69.Kieatiwong S., Nguyen L.W., Hebert V.R., Hackett M., Miller G.C, Miille M.J. and Mitzel R.“Photolysis of chlorinated dioxins in organic solvents and on soils”Environ. Sci. Technol. 24, 1575-1580.,1990
70.McPeters A.L. and Overcash M.R.“Demonstration of photodegradation by sunlight of 2,3,7,8- tetrachlorodibenzo-p-dioxin in 6 cm soil columns”Chemosphere 27, 1221-1234.,1993
71.Wipf H.K., Homberger E., Neuner N. and Schenker F.“In Cattabeni, F., Cavallaro, A., and Galli, G., eds. Dioxin – toxicological and chemical aspects. SP Medical & Scientific Books, a division of Spectrum Publications”New York, USA. pp 201-217.,1978
72.Miller G.C., Hebert V.R., Miille M.J., Mitzel R. amd Zepp R.G. “Photolysis of octachlorodibenzo-p-dioxin on soils: production of 2,3,7,8-TCDD”Chemosphere 18, 1265-1274.,1989
73.Dung M.H., O'Keefe P.W.“Comparative rates of photolysis of polychlorinated dibenzofurans in organic solvents and in aqueous solutions”Environ Sci Technol, 28(4), 549-54.,1994
74.Friesen, K.J., Foga, M.M. and Loewen, M.D.“Aquatic photodegradation of polychlorinated dibenzofurans: rates and photoproduct analysis”Environ. Sci. Technol. 30, 2504-2510.,1996
75.Friesen, K.J., Muir, D.C.G. and Webster, G.R.B.“Evidence of sensitized photolysis of polychlorinated dibenzo-p-dioxins in natural waters under sunlight conditions”EnvironSci. Technol. 24, 1739-1744.,1990
76.Dougherty, E.J., McPeters, A.L., Overcash, M.R. and Carbonell, R.G.“Theoretical analysis of a method for in situ decontamination of soil containing 2,3,7,8-tetrachlorodibenzo-p-dioxin. Environ”Sci. Technol. 27, 505-515.,1993
77.Vollmuth, S.,Zajc A. and Niessner R.“ Formation of polychlorinated dibenao-p-dioxins and polychlorinated dibenzofurans during during thephotolysis of pentachlorophenol-Containing water” Environ Sci. Technol,pp.1145-1149.,1994
78.Wu C.H. and Ng H. Y. “Photodegration of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans: Direct photolysis and photocatalysis processes ”Journal of Hazardous Materials ,151(2-3),507-514,2008