臺灣博碩士論文加值系統

本研究主要目的為探討電動力復育技術運用在現地實場上，其去除土壤中重金屬污染物之成效，並尋求影響電動力系統處理成效之因子及經濟效益。試驗以現地鉛污染土壤為目標污染物，先將實場土壤送入實驗室，進行小型模場之試驗，了解其處理成效與電化學反應現象，如電滲透流、離子遷移、電解作用等，進而將系統放大至現地規模，分別處理位在台中縣及南投市污染場址的土壤。操作參數包括：系統操作液(0.01M EDTA-2Na、0.01M Na2CO3)、電極板 (陽極：石墨板、陰極：不鏽鋼板)、電壓梯度1 V cm-1、定電流10A、定電壓80V等。在整治過程中，針對系統中(1)操作液之pH、導電度值、鉛濃度、(2)土壤pH、導電度值、鉛濃度、(3)電流、電壓、溫度及肥力分析試驗 (Ca、Mg、K、Na、F、Mn、Cu、Zn、P、OM、CEC)等進行分析監測，藉此了解此技術對現地受鉛汙染土壤處理之成效並估算其耗電量等成本。
實驗結果顯示，在烏日場址經過56天處理時間，土壤平均鉛濃度可從7190 mg Kg-1降至約2050 mg Kg-1，去除效率約可達72%。而在南投場址目前僅進行14天處理時間，土壤平均鉛濃度由7246 mg Kg-1降至約6647mg Kg-1，去除效率約可達10%，系統仍持續操作中。此外，由實驗可發現，電動力系統以循環方式操作並以0.01M Na2CO3及0.01M EDTA作為操作液時，其土壤並沒有酸化現象產生。
在操作成本方面，以烏日場址為例，系統對於1.0平方公尺的鉛污染土壤每去除1%所需的操作電費約為 8.82元。若以移除100mg Kg-1 Pb所需之操作費用約為12.6元。

The purpose of this study is to discuss the removal efficiency of heavy metal pollutants in the soil and economic cost by the in-situ pilot-scale electrokinetics. First, it will proceed the removal efficiency experiment of lead form the in-situ soil by the small pilot-scale electrokinetics in laboratory. It is to understand the electrochemical phenomenons of the electro-osmosis flow, ion migration and electrolysis effectiveness etc. Second, it will proceed the in-situ experiment in taichung and nantou that the operating parameters include: system electrolyte (0.01M EDTA-2Na, 0.01M Na2CO3), electrode material (Anode: graphite plate, Cathode: stainless steel plate), the voltage gradient, constant current and constant voltage are 1 V cm-1, 10A and 80V, respectively. In the remediation process, it will be analysis and monitoring that (1) the pH and conductivity values and lead concentration of the system electrolyte, (2) the pH and conductivity values and lead concentration of the soil, (3) current, voltage, temperature and fertility test (Ca、Mg、K、Na、F、Mn、Cu、Zn、P、OM、CEC). All of them to understand the removal efficiency of lead in the in-situ soil by electrokinetics and to count the power consumption costs.
Form the experimental results show, passed through 56 days treatment, the mean concentration of lead in the soil was from 7190 mg Kg-1 to 2050 mg Kg-1 in wuri site. The removal efficiency is around 72%. In nantou site, the mean concentration of lead in the soil was from 7246 mg Kg-1 to 6647 mg Kg-1 that removal efficiency about 10% by 14 days treatment. In addition, the soil not happened the acidification in the electrokinetics with the 0.01M Na2CO3 and 0.01M EDTA operated.
In the aspect of tlhe operating costs that example of the wuri site. The 1% removal efficiency of lead per 1.0 m2 is around NT. 8.82 dollars. It needs NT. 12.6 dollars to remove 100 mg Kg-1 Pb.

中文摘要 I
ABSTRACT II
誌謝 IV
目錄 V
表目錄 VII
圖目錄 IX
第一章 緒論 1
1-1研究緣起 1
1-2研究目的 3
第二章 文獻回顧 4
2-1台灣地區土壤重金屬污染之概況 4
2-2重金屬鉛之相關介紹 8
2-2-1鉛之用途及其可能污染來源 8
2-2-2重金屬現行法規管制標準及鉛之物化特性 11
2-2-3重金屬鉛對土壤環境及人體之影響 13
2-3電動力技術之介紹 15
2-3-1電動力法之原理與反應機制 16
2-3-2影響電動力技術操作之因子 21
2-4電動力技術整治重金屬汙染土壤之相關文獻回顧 27
第三章 試驗材料與方法 30
3-1 研究架構 30
3-2 電動力法(CEEK)整治鉛重金屬試驗室規模 32
3-2-1 電動力法(CEEK)整治鉛重金屬試驗室規模 (實驗方法與設備) 36
3-2-2 電動力法(CEEK)整治鉛重金屬試驗室規模 (樣品採樣及分析) 39
3-3 電動力法(CEEK)整治鉛重金屬烏日場址模場規模試驗 40
3-3-1電動力法(CEEK)整治鉛重金屬烏日場址模場規模試驗 (實驗方法與設備) 43
3-3-2電動力法(CEEK)整治鉛重金屬烏日場址模場規模試驗 (樣品採樣及分析) 47
3-4 電動力法(CEEK)整治鉛重金屬南投場址模場規模試驗 49
3-4-1電動力法(CEEK)整治鉛重金屬南投場址模場規模試驗 (實驗方法與設備) 52
第四章 結果與討論 53
4-1電動力法 ( CEEK )處理鉛重金屬試驗室規模之成效 53
4-1-1土壤pH及導電度變化 53
4-1-2土壤中鉛污染物濃度變化 55
4-1-3操作液中鉛濃度、pH值、導電度之變化 57
4-2電動力法 ( CEEK )整治鉛重金屬烏日模場之成效 60
4-2-1土壤pH及導電度變化 60
4-2-2操作液pH及電導度變化 61
4-2-3烏日模場土壤及操作液鉛濃度變化 62
4-2-4烏日模場系統中電流、電壓及溫度變化 64
4-2-5烏日模場系統操作結束後種植情形 66
4-3電動力法 ( CEEK )整治鉛重金屬南投模場試驗14天之成效 67
4-3-1南投模場土壤pH值及導電度變化 67
4-3-2南投模場土壤中鉛濃度變化 69
4-3-3南投模場操作液中鉛濃度、pH及導電度之變化 71
4-3-4南投模場系統電流、電壓及溫度之變化 73
4-4南投及烏日場址土壤肥力試驗分析比較 75
第五章 結論與建議 78
5-1結論 78
5-2建議 80
第六章 參考文獻 81

表目錄
表2-1台灣地區土壤重金屬含量等級區分表 ................................................... 6
表2-2台灣地區土壤污染調查統計表 ............................................................... 7
表2-3事業污染源與主要污染物質種類 ........................................................... 9
表2-4土壤中重金屬與有機污染物來源總表 ................................................. 10
表2-5台灣地區土壤重金屬污染物之監測基準及管制標準 ......................... 11
表2-6重金屬在土壤及植物中的臨界毒物 ..................................................... 14
表2-7重金屬對作物及人體的影響 ................................................................. 14
表2-8不同金屬與EDTA之錯合穩定常數 ..................................................... 23
表2-9電動力技術處理受鉛重金屬污染土壤之相關文獻 ............................. 28
表3-1電動力系統之操作參數.......................................................................... 35
表3-2土壤基本性質分析 .................................................................................. 36
表3-3實驗試藥 .................................................................................................. 37
表3-4實驗儀器設備製造商及型號 ................................................................. 38
表3-5土壤基本性質 (烏日場址) ..................................................................... 44
表3-6烏日現地試驗所使用之試藥 ................................................................. 46
表3-7南投現地模場採樣位置土壤物化特性及鉛污染濃度 ......................... 52
表4-1土壤鉛污染5個樣區鉛濃度及其去除率 ............................................. 71
表4-2南投場址之土壤於處理前後的肥力元素含量 ..................................... 76
表4-3烏日場址之土壤於處理前後的肥力元素含量 ..................................... 76
表4-4土壤養分分級表 ...................................................................................... 77


圖目錄
圖2-1 電動力法處理土壤污染物程序示意圖 ................................................ 15
圖2-2 電雙層外緣之電滲透流示意圖 ............................................................ 17
圖2-3 系統中離子遷移示意圖......................................................................... 19
圖2-4 電泳現象示意圖 ..................................................................................... 20
圖3-1 研究架構 ................................................................................................. 31
圖3-2 電動力法整治重金屬污染土壤試驗室規模裝置示意圖 .................... 33
圖3-3 電動力法(CEEK)整治重金屬污染土壤烏日現場安裝示意圖 ........... 41
圖3-4 電動力法(CEEK)現場不透水夾層安裝示意圖 ................................... 42
圖3-5 電動力法整治重金屬污染土壤烏日模場採樣位置示意圖 ................ 44
圖3-6 電動力法(CEEK)整治重金屬污染土壤南投現場安裝示意圖 ........... 50
圖4-1 污染土壤pH隨操作時間變化圖.......................................................... 54
圖4-2 污染土壤導電度隨操作時間變化圖 .................................................... 54
圖4-3 鉛污染土壤濃度變化圖......................................................................... 56
圖4-4 操作液中鉛濃度變化圖......................................................................... 58
圖4-5 操作液pH值變化圖 .............................................................................. 58
圖4-6 操作液導電度變化圖............................................................................. 59
圖4-7 烏日模場土壤pH及導電度隨操作時間變化圖 ................................. 60
圖4-8 烏日模場操作液之pH及導電度變化圖 ............................................. 61
圖4-9 烏日模場土壤中鉛濃度變化圖 ............................................................ 63
圖4-10 烏日模場操作液中鉛濃度變化圖 ...................................................... 63
圖4-11 烏日模場系統中電流及電壓變化圖 ................................................... 65
圖4-12 烏日模場系統中操作液之溫度變化圖 .............................................. 65
圖4-13 鬼針草種植情形 ................................................................................... 66
圖4-14 鬼針草播種一週後生長情形 .............................................................. 66
圖4-15 南投模場土壤pH及導電度變化圖 ................................................... 68
圖4-16 南投模場土壤鉛濃度變化圖 .............................................................. 70
圖4-17 南投模場操作液中鉛濃度變化圖 ...................................................... 72
圖4-18 南投模場操作液中pH、導電度變化圖 ............................................ 72
圖4-19 南投模場系統電流及電壓變化圖 ...................................................... 74
圖4-20 南投模場系統中操作液溫度變化圖 .................................................. 74

林裕雄，「以電動力法處理受三氯乙烯及單氯酚污染黏質土壤之研究」，碩士論文，國立中興大學環境工程學系，台中(2000)。

鄭孟嘉，「以電化學方法處理受鎘、鉛污染土壤之研究」，碩士論文，國立台灣大學化學工程學研究所，台北 (2001)。

楊金鐘、林舜隆，「利用電動力法處理人工合成之鉛污染土壤」，第十一屆廢棄物處理技術研討會論文集，台北，第518-527 頁 (1996)。

廖盈智，「循環改良式電動力系統之電化學反應」，碩士論文，朝陽科技大學環境工程與管理系，台中 (2003)。

行政院環境保護署，「111公頃農地土壤重金屬調查與場址列管計畫」，第3-19-3-23頁，台北市 (2002)。

行政院環境保護署，「土壤及地下水汙染整治法公佈施行後過渡時期執行要點」 (2000)。

行政院環境保護署，「台灣地區土壤重金屬含量調查總報告」，(1989)。

行政院環境保護署，「農地土壤重金屬調查與場址列管計畫」，(2002c)。

行政院環境保護署，「土壤污染防治草案」，(1992)。

呂進榮、沈英宏，農地土壤重金屬調查與場址列管計劃 「100公頃農地農地土壤重金屬調查與場址列管計劃」，計畫編號：EPA-90-GA13-03-90A285，(2002)。

行政院環境保護署，「土壤污染監測基準」，(2001)。

行政院環境保護署，「土壤污染管制標準」，(2001)。

劉仁煜，「土壤粒徑篩分對污染土壤重金屬移除效率之影響」，碩士論文，朝陽科技大學環境工程與管理系，台中 (2007)。

陳武清，「酸淋洗土壤中重金屬之研究」，碩士論文，元智大學 (1999)。

卓英仁，我國土壤污染現況分析及防治政策之研究，環保通訊雜誌社，台北(1988)。

翁誌煌，「受有機物污染廠址之物化整治技術研究：電滲透法整治有機污染廠址之研究 (第二年)」，行政院國科會專題研究計畫成果報告 (1998)。

劉永章、葛煥彰，「電動力現象的基本理論」，化工，第四十五卷，第二期，第77-83 頁 (1998)。

楊金鐘和林舜隆，「利用電動力處理人工合成之鉛汙染土壤」，第十一屆廢棄物處理技術研討會論文集，台北，第518-527頁 (1996)。

林裕雄，「以電動力法處理受三氯乙烯及單氯酚污染黏質土壤之研究」，碩士論文，國立中興大學環境工程學系，台中(2000)。

劉奇岳，「電動力-Fenton法現地處理三氯乙烯及4-氯酚污染土壤之最佳操作條件探討」，碩士論文，國立中山大學環境工程研究所，高雄 (1999)。

洪肇嘉、吳惠銘、紀吉鴻、陳錕容，「電動力復育鉻、鎘、鉛污染土壤研究」，第十三屆廢棄物處理技術研討會論文集，第312-318頁，高雄 (1998)。

鄭孟嘉，「以電化學方法處理受鎘、鉛污染土壤之研究」，碩士論文，國立台灣大學化學工程學研究所，台北 (2001)。

斯克誠、駱尚廉，「土壤與地下水污染整治政策與其實務」，土木水利，第26 卷，第4 期，第50-58 頁 (2000)。

洪肇嘉、 吳惠銘，「電動法處理鉛、鉻、鎘污染土壤之研究」，碩士論文，雲林科技大學，雲林 (1999)。

譚義績、王亦森、張博文、林舜隆、洪堅仁，「電動法處理重金屬污染土壤」，農業工程學報，第48卷第4期 (2002)。
U. S. EPA,“Permeable reactive barrier technologies for contaminant remediation,”Office of Research and Development, Washington DC, EPA-600-R-98-125 (1998).

Acar, Y. B. and Alshawabkeh, A. N., “Principles of Electrokinetic Remediation,” Environmental Science & Technology, Vol. 27, No. 13, pp. 2638-2647 (1993).

Acar, Y. B., Hame, J. T., Alshawabkeh, A. N., and Gale, R. J., “Removal of Cadmium from Saturated Kaolinite by the Application of Electrical Current,” Geotechnique, Vol. 44, No. 2, pp. 239-254 (1994).

Takiyama, L., and Huang, C. P., “In-Situ Removal of Phenols from Contaminated Soil by Electro-Osmosis Process,” Proceeding of 27th Mid-Atlantic Industrial & Hazardous Waste Conference, Lehigh U., Technomic, Pub. Co, Lancaster, PA. Pp. 835-846 (1995).

Nycr, E. K., Fam, S., Kidd, D. F., Palmcr, P. L., Bocttcheer, G., Crossman, T. L., and Suthersan, S. S., In-Situ Treatment, CRC Press Inc., pp. 310-314 (1996).

Al1oway, B.J., Heavy Metal in Soils, Blackie and Son Ltd. (1990).

Smith, L. A., et al., “Remedial options for metal-contaminated sites,” CRC Press Inc., United States (1995).

Casagrand, L., “The Application of Electro-osmosis to Practical Problems in Foundations and Earthwork,” Department of Scientific and Industrial Research, Building Research, London, England, Technical Paper, No.30 (1947).
Butterfield, R., and Johnson, I. W., “The Influence of Electroosmosis on Metallic Piles in Clay,” Geotechnique, Vol. 30, pp. 17-38 (1980).

Acar, Y. B., Gale, R. J., and Hamed, J., “Electrochemical Processing of Soils：Its Potential Use in Environmental Geotechnology and Significance of pH Gradient,” 2nd International Symposium on Environmental Geotechnology, Shanghai, China, May 14-17, Envo Publishing, Bethlehem, PA Vol.1, pp. 25-38 (1989).

Khan, L. I., Pamukcu, S., Kugelman, I., “Electro-osmosis in Fine-grained Soil,” 2nd International Symposium on Environmental Geotechnology, Shanghai, China, May 14-17, Envo Publishing, Bethlehem, PA Vol.1, pp. 39-47 (1989).

Acar, Y. B. and Alshawabkeh, A. N., “Principlesof Electrokinetic Remediation,” Environmantal Science &Technology, Vol.27,NO.13, pp. 2638-2647 (1993).

Jacob, H. M., Electrokinetic Transport Phenomena, AOSTRA, Canada (1994).

Acar, Y. B., Gale, R. J., Alshawabkeh, A. N., Marks, R. E., Puppala, S., Bicka, M., and Parker, R., “Electrokinetic Remediation: Basics and Technology Status,” Journal of Hazardous Materials, Vol. 40, No. 2, pp. 117-137 (1995).

Leinz, R. W., Hoover, D. B., and Meier, A. L., “NEOCHIN: An Electrochemical
Method for Environmental Application,” Journal of Geochemical Exploration,
Vol. 64, No. 3, pp. 421-434 (1998).



Kim, S. O., Moon, S. H., Kim, K. W. and Yun, S. T., “Pilot scale on the ex site electrkinetic removal of heavy metal from municipal wastewater sludge,” Water Research, Vol. 36, pp. 4765-4774 (2002).

Pamukcu, S. and Wittle, J. K., “Electrekinetic removal of selected heavy metals from soil,” Environmental Progress, Vol. 11,NO.3,pp.241-250 (1992).

Acar, Y. B. and Alshawabkeh, A. N., “Principles of Electrokinetic Remediation,” Environmental Science & Technology, Vol. 27, No. 13, pp.2638-2647 (1993).

Brain, E. R., Berg, M. T., Thompson, J. C. and Hatfield, J. H., “Chemical Conditioning of Electrode Reservoirs during Electrokinetic Soil Flushing of Pb-Contaminated Silt Loam,”Journal of Environmental Engineering, Vol. 121, No. 11, pp. 805-815 (1995).

Yeung, A. T., “Coupled Flow Equations for Water, Electricity, and Ionic contaminants Through Clayey Soils under Hydraulic, Electrical and Chemical Gradient,” Journal of Non-Equilibrium Thermodynamics, Vol. 15, No. 3, pp. 247-267 (1990).

Yeung, A. T., and Mitchell, J. K., “Coupled Fluid, Electrical, and Chemical Flow in Soils,” Geotechnique, Vol. 43, No. 1, pp. 121-134 (1993).

Mitchell, J. K., “Condition Phenomena: from Theory to Geotechnical Practice,”
Geotechnique, Vol. 41, No. 3, pp. 299-340 (1991).


Mitchell, J. K., Fundamentals of Soil Behavior, 2nd edition, John Wiley & Sons,
New York (1993).

Yeung, A. T., Hsu, C. N., and Menon, R. M., “Physicochemical Soil-contaminant Interactions during Electrokinetic Extraction,” Journal of Hazardous Materials, Vol. 55, pp. 221-237 (1997).

Virkutyte, J., Sillanpaa, M. and Latostenmaa, P., “Electrokinetic soil remediation-critical overview,” The science of the Total Environment, Vol. 289, pp. 97-121 (2002).

Acar, Y. B. and Alshawabkeh, A. N., “Principles of Electrokinetic Remediation,” Environmental Science & Technology, Vol. 27, NO. 13, pp. 2638-2647 (1993).

Alshawabkeh, A. N. and Acar, Y. B.., “Removal of contaiminants from soil by electrokinetics A theoretical treaties,” Journal of Environmental Science and Health, Vol. 27, Part A, pp. 1835-1861 (1992).

Ottosen, L. M., Hansen, H. K., Ribeiro, A. B. and Villumsen A., “Removal of Cu、Pb and Zn in an applied electric field in calcareous and non-calcareous soils,” Journal of hazardous materials, B85, pp.291-299 (2001).

Kim, S. O., and Kim, K. W., “Monitoring of electrokinetic removal of heavy metals in tailing-soils using sequential extraction analysis,” Journal of Hazardous Materials, B85, pp. 195-211 (2001).


Darmawan and Wada, S. I., “Effect of clay mineralogy on the feasibility of electrokinetic soil decontamination technology,” Applied clay science, Vol. 20, pp. 283-293 (2002).

Acar, Y. B., Gale, R. J., Alshawabkeh, A. N., Marks, R. E., Puppala, S., Bicka, M. and Parker, R., “Electrokinetic Remediation：Basics and Technology Status,” Journal of Hazardous Materials, Vol. 40, No. 2, pp.117-137 (1995).

Vane, M. L. and Zang, G. M., “Effects of Aqueous Phase Properties on Clay Particle Zeta Potential and Electro-osmotic Permeability：Implications for Electro-kinetic Soil Remediation Processes,” Journal of Hazardous Materials, Vol. 55, No. 3, pp. 1-22 (1997).

Hamed, J. T., and Bhadra, A., “Influence of Current Density and pH on Electrokinetics,” Journal of Hazardous Materials, Vol. 55, pp. 279-294 (1997).

Chang, J. H., Qiang, Z., Huang, C. P., and Cha, D., “Electroosmotic Flow Rate: A Semiempirical Approach,” Chapter 15 in Nuclear Site Remediation: First Accomplishments of the Environmental Management Science Program, ACS Symposium Series, Vol. 778, pp. 247-266 (2000).

Chung, H. I. and Kang, B. H., “Lead removal from contaminated marine clay by electrokinetic soil decontamination,” Engineering Geology, Vol. 53, pp. 139-150 (1999).

Baraud, F., S. Tellier, and M. Astruc, “Temperature Effect on Ionic Transport During Soil Electrokinetic Treatment at Constant pH,” Journal of Hazardous Materials, Vol. 64, No.3, pp.263-281 (1999).
Nyer, E. K., Fam, S., Kidd, D. F., Palmcr, P. L., Bocttcheer, G., Crossman, T. L. and Suthersan, S. S., “In-Situ Treatment,” CRC Press Inc., Boca Raton, Florida, pp. 310-314 (1996).

Lee, H. H., and Yang, J. W., “A New Method to Control Electrolytes pH by Circulation System in Electrokinetic Soil Remediation,” Journal of Hazardous Materials, Vol. B77, pp. 227-240 (2000).

Li, Z., Yu, J. W., and Neretnieks, I., “Removal of Pb (II), Cd (II), and Cr (III) from sand by Electromigration,” Journal of Hazardous Materials, Vol. 55, No. 1-3, pp. 295-304 (1997).

Yeung, A. T., Hsu, C. N., and Menon, R. M., “EDTA-Enhanced Electrokinetic Extraction,” Journal of Environment Engineering, Vol. 122, No. 8, pp. 666-673 (1996).

Puppala, K. S., Alshawabkeh, A. N., Acar, Y. B., Gale, R, J., and Bricka, M., “Enhanced Electrokinetic Remediation of High Sorption Capacity Soil,” Journal of Hazardous Meterials, Vol. 55, PP. 221-237 (1997).