研究生: |
張士強 Matt Shih-Chiang Chang |
---|---|
論文名稱: |
次臨界水萃取整治土壤中鄰苯二甲酸酯類之可行性研究 Feasibility Study Using Subcritical Water Extraction for the Remediation of Phthalate Ester-Contaminated Soil |
指導教授: |
吳家誠
Wu, Jia-Cheng |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2002 |
畢業學年度: | 90 |
語文別: | 中文 |
論文頁數: | 132 |
中文關鍵詞: | 鄰苯二甲酸酯 、加速溶劑萃取 、次臨界水 、土壤 |
英文關鍵詞: | phthalate ester, accelerated solvent extraction, subcritical water, soil |
論文種類: | 學術論文 |
相關次數: | 點閱:256 下載:6 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
所謂環境荷爾蒙是指可能模仿或阻斷生物體正常的內分泌、增加或減少生物體內荷爾蒙濃度,進而影響了生物體體內正常荷爾蒙的功能的化學物質。常用的塑化劑鄰苯二甲酸酯類( phthalate ester, PAE),已被日本環境廳與美國環保署列為疑似環境荷爾蒙物質。也因為容易流入環境中,近年來逐漸受到世人的重視。
次臨界水的介電常數可藉由溫度與壓力的控制下來改變,在以液態水的存在下,介電常數會因溫度與壓力的上升而有明顯的下降。本研究以250℃、100 bar (經條件最佳化)的次臨界水來對土壤中的12種PAEs作萃取處理。而處理過後的土壤樣品則利用加速溶劑萃取系統(accelerated solvent extraction, ASE)來做萃取工作,再將其導入HPLC-UV做定性及定量上的分析。此分析方法對土壤中12種PAEs的準確度介於80~125 % 之間,精密度為4.54~9.16 %。方法偵測極限可達0.18(DEHP)~1.70(DEP) μg/g。
在台灣常見三種不同土系的添加分析中,次臨界水對土壤中PAEs的處理效率亦可達80~90 % 以上。顯示對土壤中的PAEs良好的移除率。用以處理土壤之水,經定量分析,發現次臨界水對部分PAEs具有分解作用,其分解機制與條件仍有研究之空間,值得探討。
Environmental Hormones are the compounds that could simulate or disrupt the functions of the hormones. They may increase or decrease the concentraction of the hormones in biological species, and affect their normal physiology. Phthalate esters (PAEs), a popular group of plasticizers, have already been categorized under Environmental Hormones by Environment Agency Government of Japan and United State Environmental Protection Agency. Because they can be easily transfered into our environment and may cause different harmful effects, people began to pay attention to them.
Dielectric constants of subcritical water are easily tunable, since they decrease significantly by raising temperature under moderate pressure, and still keeping water in the liquid state. Subcritical water under the optimized condition of 250℃ and 100 bar are used for the removal of PAEs in soil samples in our study. The subcritical-water-cleaned soil samples are extracted by accelerated solvent extraction system (ASE) and analyzed by HPLC-UV. The accuracy in term of recovery of this method for twelve PAEs in soil was in the range of 80 to 125 % ( RSD< 9.16 % ), and the method detection limits (MDL) ranged from 0.18 (DEHP) to 1.70 (DEP) μg/g.
Three types of soil collected at different sites in Taiwan have been tested. Real samples spiked with different PAEs were treated with subcritical water extraction, and the results indicated a efficiency range of 80~90 % for the removal of PAEs. Results also indicated that certain fractions of PAEs were decomposed under the conditions of subcritical water treatment. Further investigation may be needed to elucidate more information of the results. Our results show that the treatment with subcritical water for PAEs in real soil samples is highly feasible.
1.陳永仁,”環境荷爾蒙管制”,財團法人孫運璿學術基金會獎助,2001。
2.鄭顯榮,陳志銘,黃明輝, ”內分泌干擾物質(環境荷爾蒙)及持久性有機污染物之環保管制情形”,第一屆環境荷爾蒙與持久性有機污染物研討會,12-29, 2000。
3.小泉睦子和長谷川隆一,”Endocrine Disrupting Action of Environmental Chemicals on Mammals”, Nihon Yukagakkaishi, 48, 5, 431-437, 1999.
4.酒井憲司, ” Studies on endocrine-disrupting chemicals in sewage treatment”, Gesuiso Kyolaishi, 36, 445, 34-38, 1999.
5.K. R. Cooper, “Impacts of Endocrine Compounds on Reproductive Success at the Population Level”, 第一屆環境荷爾蒙與持久性有機污染物研討會,1-2, 2000。
6.R. W. Baker, “ Determination of Phthalates in Aquatic Environments”, Toxicology, 9, 319, 1978.
7.L. H. Keith, A Practical Guide and Lewis Publishers, New York, 1992.
8.EPA, “ Phthalate Esters : EPA Method 606 ”, J. Chromatogra. Sci. 27, 685, 1989.
9.” Method for Organic Analysis of Municipal and Industrial Water ”, SW846 Method 8061A, United States Environmental Protection Agency.
10.D. A. Brikholz, R. T. Coutts and S. E Hrudey,” Determination of Polycyclic Aromatic Compounds in Fish Tissue ”, J. Chromatogra., 449, 251-260, 1988.
11. T. Nielsen,” Isolation of Polycyclic Aromatic Hydrocarbons and Nitro Derivatives in Complex From Solid Samples ”, Anal. Chem., 58, 962-965, 1986.
12. T. Paschke, S. B. Hawthorne and D. J. Miller,” Supercritical Fluid Extraction of Nitrated Polycyclic Aromatic Hydrocarbons from Diesel Exhaust Particulate Matter ”, J. Chromatogra., 609, 333-340, 1992.
13. M. D. Burford, S. B. Hawthorne and D. J. Miller,” Extraction Rate of Spiked versus Native PAHs from Heterogeneous Environmental Samples Using Supercritical Fluid Extraction and Sonication in Methylene Chloride ”, Anal. Chem., 65, 1497-1505, 1993.
14. R. W. Wright, C. W. Wright, R. W. Gale and R. D. Smith,” Analytical Supercritical Fluid Extraction of Adsorbent Materials”, Anal. Chem., 59, 38-44, 1987.
15. L. A Vlorica and R. Young,” Microwave-Assisted Extraction of Organic Compounds from Standard Reference Soils and Sediments ”, Anal. Chem., 66, 1097-1106, 1994.
16.H. L. Bohn, B. L. McNeal and G. A. O’connor, 洪崑煌、王光明、陳尊賢、賴朝明、何聖賓、李達源合譯,“SOIL CHEMISTRY, 土壤化學”,國立編譯館出版,1996。
17.郭魁士, “土壤學”, 中國書局印行, 1986。
18.李俊福, “土壤中的有機毒性物質”, 科學月刊, 第26卷, 第三期。
19. R. Gachter and H. Muller, “ Plastics Additives Handbool, Hanser Publishers ”, New York, 1985.
20. D. B. Peakall,” Exposure of Newborn Infants to Plasticizers - Plasms Levels of Di-(2-ethylhexyl) Phthalate and Mono-(2-ethylhexyl) Phthalate During Exchange Transfusion ”, Residue Rev., 54, 1-41, 1975.
21. S. R. Murphy and B. L. Wadey, ” Phthalate Esters Plasticizers: A New Class of Marine Pollutant ”, J. Vinyl. Technol., 10(3), 121-124, 1988.
22.經濟部工業局, “ 86年工業發展年鑑 ”, 工業發展年鑑, 民國86年。
23. R. Herring and C. L. Beriing,” Effects of Phthalate Esters on Plant Seedlings and Reversal by Soil Microorganism ”, Bull. Environ. Contam. Toxicol. , 40, 626-632, 1988.
24. K. Suyama and S Addachi,” Gas-Liquid Chromatographic Retention of Phthalate and Transesterified Products in Terms of Equivalent Chain Length Values of Fatty Acid Methyl Esters ”, J. Chromatogra., 294, 339-343, 1984.
25. O. L. Jackson, Jr. and J. M. Barbara,” Plasticizers in Pacifiers: Direct Determination by FAB-MS ”, Anal. Chem., 59(22), 1323A- 1325A, 1987.
26. Environment Health Criteria 131, “ Diethylhexyl phthalate ”, IPCS, 1992.
27. C. S. Giam, H. S. Chau and G. S Neff, ” Rapid and Inexpensive Method for Detection of Polychlorinated Biphenyl and Phthalates in Air ”, Anal. Chem., 47(13), 2319-2320, 1975.
28. 山畸 裕康 和桑田 一弘,” Determination of Phthalates in Air”, Bunseki Kagaku, 26(1), 1-5, 1977.
29. K. F. Sullivan, E. L. Atlas and C. S Griam,” Adsorption of Phthalate Acid Esters from Seawater ”, Environ. Sci. Technol., 16, 428-432, 1982.
30. A. Thuren,” Determination of Phthalate in Aquatic Environments ”, Bull. Environ. Contam. Toxical., 36, 33-40, 1986.
31. J. C. Peterson and D. H. Freeman,” Variations of Phthalate Ester Concentrations in Sediments From the Chester River, Maryland ”, Intern. J. Environ. Anal. Chem., 18, 237-252, 1984.
32. M. J. Schouton, U. A Th. Brinkman and J. W. C. Peereboom,” Liquid Chromatographic Analysis of Phthalate Esters in Dutch River Water ”, Intern. J. Environ. Anal. Chem., 7, 13-23, 1979.
33. K. Holadova and J. Hajslova,” A Comparison of Different Ways of Sample Preparation for the Determination of Phthalic Acid Esters in Water and Plant Matrices ”, Intern. J. Environ. Anal. Chem.,59, 43-57, 1995.
34. J. C. Gaston Wu,” Determination of Trace Phthalate Esters Using HPLC with Programmed Elution and On-Line Concentration ”, J. Environ. Sci. Health, A26, 1363-1385, 1991.
35. H. E. Schuwartz, C. J. M. Anzion, H. P. M. Van-Vliet, J. W. C. Peereboom and U. A Th. Brinkman,” Analysis of Phthalate Esters in Sediments from Dutch Rivers by means of High Performance Liquid Chromatography ”, Intern. J. Environ. Anal. Chem., 6, 133-144, 1979.
36. D. J. Russell and B. McDuffie,” Analysis for Phthalate Esters in Environmental Samples: Sepatation from PCB’s and Pesticides Using Dual Column Liquid Chromatography ”, Intern. J. Environ. Anal. Chem., 15, 165-79, 1983.
37. P. W. Albro, S. T. Jordan, J. L. Schroeder and J. T Corbett,” Chromatographic Separation and Quantitative Urine of Laboratory Animals ”, J. Chromatogra., 244, 65-79, 1982.
38. J. Vessman and G. Rietz,” Determination of Di(ethylhexyl) Phthalate in Human Plasma and Plasma Proteins by Electron Capture Gas Chromatography ”, J. Chromatogra., 100, 153-163, 1974.
39. C. Persiinnii and P. Cukor,” Liquid Chromatographic Method for the Determination of Phthalate Esters ”, J. Chromatogra., 109, 413-417, 1975.
40. F. L. Mayer, Jnn., D. L. Stalling and J. L. Johnson,” Phthalate Esters as Environmental Contaminants ”, Nature, 238, 411-413, 1972.
41. C. S. Giam, H. S. Chan and G. S. Neff.,” Sensitive Method for Determination of Phthalate Ester Plasticizers in Open-Ocean Biota Samples ”, Anal. Chem., 47, 2225-2229, 1975.
42. K. Sreenivasan,” High-Performance Liquid Chromatographic Method for the Simultaneous Separation and Determination of three additives in poly(vinyl chloride) ”, J. Chromatogra., 357, 433-435, 1986.
43. H. Shintani,” Determination of Phthalic Acid, Mono-(2-ethylhexyl) Phthalate and Di-(2-ethylhexyl) Phthalate in Human Plasma and Blood Products ”, J. Chromatorgra., 337, 279-290, 1985.
44. G. M. Pollack, R. L. Slanughter, J. F. Buchaman and D. D. Shen,” High-Performance Liquid Chromatographic Procedure for the Determination of Di-(2-ethylhexyl) Phthalate in Human Blood Specimens ”, J. Chromatogra., 311, 101-108, 1984.
45. I. Gerlai and J. Pinter,” Determination of DEHP in Blood Products Stored in Plastic Bags by HPLC ”, Chromatogra., 24, 403-406, 1987.
46. V. V Bhujle, P. D Nair and K. Sreenivasan,” High-Performance Liquid Chromatographic Determination of Di(2-ethylhexyl) Phthalate in Blood Stored in PVC Blood Bags ”, Analyst, 109, 177-178, 1984.
47. D. C. M. Squirrell,” Analysis of Additives and Process Residues in Plastics Materials ”, Analyst., 106, 1042-1056, 1981.
48. 張碧芬、袁紹英,”鄰苯二甲酸酯類環境荷爾蒙對生物的影響”,第31期。
49. C. A. Staples, and D. R. Peterson, Thomas F. Parkerton and William J. Adams, ” The Environmental Fate of Phthalate Esters: A Literature Review ”, Chemosphere, 35, 667-749, 1997
50. M. Ishida, K. Suyama and S. Adachi,” Background Contamination by Phthalate Commonly Encountered in the Chromatographic Analysis of Liquid Samples ”, J. Chromatogra., 189, 421-424, 1980.
51. 張碧芬,”環境荷爾蒙-塑膠添加物 鄰苯二甲酸酯類在環境中的流佈”。
52. R. C. Scoott, P. H. Dugard, J. D. Ramsey and C. Rhodes,” In Vitro Absorption of Some o-Phthalate Diesters Through Human and Rat Skin ”, Environ. Health Pers., 74, 223-227, 1987.
53. P. O. J. Sjoberg, U. G. Bonddesson, E. G. Sedin and J. P. Gustaison,” Exposure of Newborn Infants to Plasticizers-Plasms Levels of Di-(2-ethylhexyl) Phthalate and Mono-(2-ethylhexyl) Phthalate During Exchange Transfusion ”, Transfusion, 25(5), 424-428, 1985.
54. V. B. Stein, T. A. Amin and R. S. Narang,” Sensitive Method for Determination of Phthalate Ester Plasticizers in Open-Ocean Biota Samples ”, J. Assoc. off. Anal. Chem., 70(4), 721-723, 1987.
55. V. Lopez-Avila, J. Milanes, N. S. Dodhiwala and L. F. Beckert,” Cleanup of Environmental Sample Extracts Using Florisil Solid-Phase Extraction Cartridges ”, J. Chromatogra. Sci., 27, 209-215, 1989.
56. Test Method for Evaluating Solid Waste, Method 3545, EPA SW-846, 3rd ed., Update III US GPO, Washington, DC., July, 1995.
57. B. E Richer, J. L. Ezzell, K. A. Roberts and D. W Later,” An Accelerated Solvent Extraction System for the Rapid Preparation of Environment Organic Compounds in Soil ”, Am. Lab., 27, 24-28, 1995.
58. 陳倩雯,快速溶劑萃取系統與高效率液相層析介面在分析土壤中多苯環芳香烴化合物之方法研究,國立台灣師範大學研究所碩士論文,吳家誠教授指導,1999。
59. 陳揖遜,以超臨界流體萃取/同位素稀釋質譜進行土壤中的多苯環芳香烴化合物分析,國立台灣師範大學化學研究所碩士論文,吳家誠教授指導,1996。
60. M. Ellen and P. Mcnally,” Advance in Environmental SFE”, Anal. Chem., 67, 221R-255R, 1995.
61. R. H. Perry, D. W. Green, J. O. Maloney, “Perry’s Chemical Engineer’s Handbook ”, 6th ed, Chapter 3, 1984.
62. B. E. Richer,” B. A Jones.; J. L. Ezzell, and N. L. Poter,” Accelerated Solvent Extraction: A Technique for Sample Preparation ”, Anal. Chem., 68, 1033-1039, 1996.
63. K. S. Pitzer, L. Brewer and Thermodynamics, 2 ed.; McGraw-Hill: New York, Chapter 18, 1961.
64. T. Sekine and Y. Hassegawa,“ Solvent Extraction Chemistry ”, Marcel Dekker: New York, 1997.
65. G. C. Pimentel, A. L. McClellan, “ The Hydrogen Bond ”, Freeman: San Francisco, 1960.
66. 李惠美,加速溶劑萃取技術配合同位素稀釋氣相層析質譜法進行土壤中三十五種多苯環芳香烴化合物之分析方法研究,國立台灣師範大學化學研究所碩士論文,吳家誠教授指導,1997。
67. 李迪雯,加速溶劑萃取技術配合同位素稀釋氣相層析質譜儀法進行大氣塵粒中三十五種多苯環芳香烴化合物之分析方法研究,國立台灣師範大學研究所碩士論文,吳家誠教授指導,1997。
68. 許裕昌,加速溶劑萃取技術配合同位素稀釋氣相層析質譜法分析土壤及底泥中十二種鄰苯二甲酸酯之方法研究,國立台灣師範大學化學研究所碩士論文,吳家誠教授指導,1997。
69. X. Lou, H-G. Janssen and C. A. Cramers,” Parameters Affecting the Accelerated Solvent Extraction of Polymeric Samples ”, Anal. Chem., 69, 1598-1603, 1997.
70. N. Saim, J. R. Dean, Md. P. Abdullaah and Zakaria,“ An Experimental Design Approach for the Determination of Polycyclic Aromatic Hydrocarbons from Highly Contaminated Soil Using Acceleated Solvent Extraction ”, Anal. Chem., 70, 420-424, 1998.
71. O. P. Heemken, N. Theobald and B. W. Wenclawiak,“ Comparison of ASE and SFE with Soxhlet, Sonication and Methanolic Saponification Extractions for the Determination of Organic Micropollutants in Marine Particulate Matter ”, Anal. Chem., 69, 2171 -2180, 1997.
72. J. R. Dean,“ Acceletated Solvent Extraction of Polycyclic Aromatic Hydrocarbons from Contaminated Soil ”, Analytical Communications, 33, 191-192, 1996.
73. D. V. Kenny and S. V. Olesik,” Extraction of Bituminous Coal Fly Ash for Polynuclear Aromatic Hydrocarbons: Evaluation of Modified and Unmodified Supercritical Fluid Extraction, Enhanced-Fluidity Solvents and Accelerated Solvent Extraction”, J. Chromatogr. Science, 36, 66-72, 1998.
74. D. V. Kenny and S. V. Olesik,“ Extraction of Lignite Coal Fly Ash for Polynuclear Aromatic Hydrocarbons” Modified and Unmodified Supercritical Fluid Extraction, Enhanced-Fluidity solvents and Accelerated Solvent Extraction ”, J. Chromatogr. Science, 36, 59-65, 1998.
75. A. Kreisselneier and H. W. Durbeck,” Comparison between Accelerated Solvent Extraction and Traditional Extraction Methods for the Analysis of the Herbicide Diflufenican in Soil ”, J. Chromatogr. A, 765, 121-125, 1997.
76. M. Okihashi, H. Obana and S. Hori,“ Determination of Organoph- osphorus Pesticides in Foods Using an Accelerated Solvent Extraction System ” Analyst, 122, 217-220, 1997.
77. H. Obana, K. Kikuchi, M. Okihashi and S. Hori,“ Determination of N-methylcarbamate Pesticides in Foods Using an Accelerated Solvent Extraction with a Minic Column Cleanup ”, Analyst, 123, 711-714, 1998.
78. K. Schafer,“ Accelerated Solvent Extraction of Lipids for Determining the Fatty Acid Composition of Biological Material ”, Analytical Chimica Acra, 358, 69-77, 1998.
79. B. Erland, J. Mattias, M. Lennart, K. Lar, E. Jonaas and T. Arne, J. Liq. Chromatogr. Relat. Technol., 21(4), 535-549, 1998.
80. D. J. Miller and S. B.Hawthorne,” Method for determing the solubilities of hydrophobic organics in subcritical water ”, Anal. Chem. , 70, 1618-1621,1998.
81. S. B. Hawthorne, S. Trembley, C. L. Moniot, C. B. Grabanski and D. J. Miller,“ Static subcritical water extraction with simultaneous solid- phase extraction for determining polycyclic aromatic hydrocarbons on environmental solids “, J. Chromatogr. A, 886, 237-244, 2000.
82. V. Fernandez-Perez and M.D. Luque de Castro,“ Micelle formation for improvement of continuous subcritical water extraction of polycyclic aromatic hydrocarbons in soil prior to high-performance liquid chromatography–fluorescence detection ”, J. Chromatogr. A, 902, 357-367, 2000.
83. M. S. S. Curren and J. W. King,“ Solubility of Triazine pesticides in pure and modified subcritical water “, Anal. Chem., 73, 740-745, 2001.
84. S. B. Hawthorne, C. B. Grabanski, K. J. Hageman and D. J. Miller, “ Simple method for polychlorinated biphenyl concentractions on soils and sediments using subcritical water extraction coupled with solid-phase microextraction ”, J. Chromatogr. A, 814, 151-160, 1998.
85. K. J. Hageman, L. Mazeas, C. B. Grabanski, D. J. Miller and S. B. Hawthorne, “ Coupled subcritical water extraction with solid-phase microextraction for determining semivolatile organics in environmental solids “, Anal. Chem., 68, 3892-3898, 1996.
86. R. M. Smith and R. J. Burgess, “ Superheated water as an eluent for reversed-phase high-performance liquid chromatography ”, J. Chrom- atogr. A, 785, 49-55, 1997.
87. 馬根善,”第一部分/自然水體之錯化包容力研究;第二部分/程式化流洗式線上管柱前濃縮高速液層析法對微量鄰苯二甲酸酯類之測定研究,國立臺灣師範大學化學研究所碩士論文,吳家誠教授指導,1990。
88. 邱燕萍,”快速溶劑萃取系統介面高效率液相層析儀在分析土壤中鄰苯二甲酸酯之方法研究”, 國立臺灣師範大學化學研究所碩士論文,吳家誠教授指導,2000。
89. P. Krammer and H. Vogel,” Hydrolysis of esters in subcritical and super- critical water “, J. Supercritical fluids, 16, 189-206, 2000.
90. R. L. Holiday, B. Y. M. John and J. W. Kolis,“ Organic synthesis in subcritical water oxidation of alkyl aromatics “,J. Supercritical fluids, 12, 255-260, 1998.
91. H. Tagaya, K. Katoh, J. Kadokawa and K. Chiba,“ Decomposition of polycarbonate in subcritical and supercritical water “, Polymer Degradation and Stability, 64, 289-292, 1999.
92. T. Funazukuri and M. Takahashi,“ Decomposition of 2-aminoethanol in sub- and supercritical water with/without hydrogen peroxide “, Fuel, 78, 78, 1117-1119, 1999.
93. 陳尊賢,”污染土壤之整治技術及評估” http://lab.ac.ntu.edu.tw/soilsc/