臺灣博碩士論文加值系統

烏腳病是一種於1960年代流行於台灣西南沿海一帶的心血管疾病;對於烏腳病的致病因素，一般認為是和居民所飲用的井水中之砷和腐植質有關; 然而，烏腳病的致病因素仍在爭辯的階段。烏腳病的研究多著重於流行病學和動物試驗方面，對於砷在自然水體中或受污染土壤中之物種的了解甚少。因此，本論文研究之主要目的是利用同步輻射光源的延伸性X光吸收精細結構(Extended X-ray absorption fine structural, EXAFS) 和X光吸收近邊緣結構(X-ray absorption near edge structural, XANES)光譜，探討地下水和含砷金礦渣中的砷物種之化學結構。
砷吸附於氧化鋁或二氧化矽之實驗在固定床式反應器進行，實驗結果顯示氧化鋁對砷的吸附是一可逆且無選擇性的反應，但29 Si 的核磁共振光譜圖顯示，砷主要吸附於二氧化矽的Q3 位置上。
利用EXAFS和XANES光譜研究烏腳病區地下水和含砷金礦渣於電化學反應中的砷物種化學結構，XANES光譜指出五價砷是烏腳病區地下水中的主要物種 ; EXAFS光譜分析顯示地下水中的砷之As-O平均鍵長為1.67-1.71 A，第二層之As-C 和As-As 平均鍵長分別為2.84 和3.18-3.29 A，指出烏腳病區井水中的砷和腐植質螯合。在含砷金礦渣中的As-O 和As-As 平均鍵長分別為1.78 和3.21 A，配位數分別為3.6和2.2，但受到電動勢影響使As-O 和As-As鍵長增加0.01 A。
本研究是利用同步輻射光源探討在複雜環境固體樣品中之微量有害重金屬之分子結構實例，並且提出另一種可能在50年前造成台灣西南岸地區之烏腳病流行的可能毒性物質。
關鍵字: 砷、烏腳病、電化學、29 Si 的核磁共振光譜、EXAFS、XANES。

The blackfoot disease is a unique peripheral vascular disease occurred in the southwest coast of Taiwan in 1960s. Arsenic and the fluorescent substances are generally believed to be the two main possible etiology factors of blackfoot disease in the ground water that was drunk by local inhabitants. However, there is still a debate for the cause of the blackfoot disease. Studies of the blackfoot disease in Taiwan have focused attention on the epidemiology and animal tests. Speciation of As in natural waters or contaminated soils is not well understood. Thus, the main objective of this work was to study the chemical structure of As in the ground water and As embedded in the complex matrix of a gold tailing by EXAFS and XANES spectroscopies.
Adsorption of As species on γ-Al2O3 and SiO2 was conducted in a packed bed reactor. Experimentally, we found that the adsorption was reversible and not selective for energetic sites on Al2O3. However, the 29 Si MAS NMR spectra suggested that As might be adsorbed on the Q3 sites ((HO) Sio(OSi)3) of SiO2.
Extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies were used to investigate the chemical form of As species in the ground water of the blackfoot disease area and the As-embedded gold tailing during electrokinetic remediation (EKR) process. By XANES, we found that As(Ⅴ) was the main As species in the ground water of the blackfoot disease area. EXAFS spectra also showed that As in ground water possessed As-O (1st shell) bond distances of 1.67-1.71 A. In the second shells of As, the average bond distances of As-C and As-As were 2.84 and 3.18-3.29 A, respectively. It seemed that As was chelated with humic substances in the ground water of the blackfoot disease area. The bond distances of As-O and As-As in the tailing were 1.78 A and 3.21 A with coordination numbers (CNs) of 3.6 and 2.2, respectively. However, possibly due to the perturbation of As by electric field, the bond distances of As-O and As-As were increased slightly by (0.01 A) in the EKR process.
Key words: As, blackfoot disease, EKR, 29 Si MAS NMR, EXAFS, XANES.

CONTENT
Page
授權書 I
簽署人須知 II
中文摘要 III
ABSTRACT V
誌謝 VI
CONTENT VII
LIST OF FIGURES IX
LIST OF TABLES XI
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 LITERATURES SURVEY 4
2.1 Arsenic Sources 4
2.2 Arsenic Chemistry 6
2.3 Arsenic in Environment 8
2.4 Human Health Concern of Arsenic 13
2.5 Blackfoot Disease 18
2.6 Humic Substances 19
CHAPTER 3 EXPERIMENTAL METHODS 23
3.1 Adsorption Reaction 23
3.1.1 As adsorption experiments 23
3.1.2 Ground water adsorption reaction 23
3.1.3 As and humic acid adsorption reaction 24
3.2 Electrokinetic Remediation 24
3.3 Characterization of As Species 24
3.3.1 X-ray Diffraction Spectroscopy (XRD) 24
3.3.2 Fourier Transmission Infared Resonance (FTIR) spectroscopy 27
3.3.3 Solid State Nuclear Magnetic Resonance (SS NMR) 27
3.3.4 Extended X-ray Absorption Fine Structural (EXAFS) 27
CHAPTER 4 RESULTS AND DISCUSSION 31
4.1 Speciation of As adsorbed on Al2O3 31
4.2 Speciation of As Adsorbed on SiO2 38
4.3 Speciation of As-Humic Acid Adsorbed on Al2O3 50
4.4 Speciation of As in the Ground Water of the Blackfoot Disease Area 61
4.5 In-situ EXAFS Study of As in Electrokinetic Remediation 69
CHAPTER 5 CONCLUSIONS 78
REFERENCES 80

References
1. Bruce A. Manning and Sabine Goldberg, "Adsorption and Stability of Arsenic (Ⅲ) at the Clay Mineral-Water Interface", Environmental Science & Technology, Vol. 31, No. 7, 2005-2011, 1997.
2. Scott Fendorf, Matthew J. Eick, Paul Grossl and Donald L. Sparks, "Arsenate and Chromate Retention Mechanisms on Goethite. 1. Surface Structure", Environmental Science & Technology, Vol. 31, No. 2, 315-320, 1997.
3. Wen-Ping Tseng, "Effects and Dose-Response Relationships of Skin Cancer and Blackfoot Disease with Arsenic", Environmental Health Perspectives, Vol. 19, p. 109-119, 1977.
4. Shun-Long Chen, Shiaan R. Dzeng, Mo-Hsiung Yang, Kong-Hwa Chiu, Guan-Ming Shieh and Chien M. Wai, "Arsenic Species in Ground waters of the Blackfoot Disease Area, Taiwan", Environmental Science & Technology, Vol. 28, No. 5, 877-881, 1994.
5. C. -J. Chen, C. W. Chen, M. -M. Wu and T. -L. Kuo, "Cancer potential in liver, lung, bladder and kidney due to ingested inorganic arsenic in drinking water", Br. J. Cancer, Vol. 66, 888-892, 1992.
6. John F. Ferguson and Jerome Gavis, "A Review of the Arsenic Cycle in Natural Water", Water Research, Vol. 6, p. 1259-1574, 1972.
7. F. J. Lu, "Blackfoot disease: arsenic or humic acid? ", Lancet, p.115-116, 1990.
8. F. J. Lu, S. R. Shih, T. M. Liu and S. H. Shown, "The Effect of Fluorescent Humic Substances Existing in the Well Water of Blackfoot Disease Endemic Area in Taiwan on Prothrombin Time and Activated Partial Thromboplastin Time in Vitro", Thrombosis Research, Vol. 57, p.747-753, 1990.
9. F. J. Lu, T. S. Huang, Y. S. Lin, Victor Fei Pang and S. Y. Lin, " Peripheral Vasculopathy in Rats Induced by Humic Acid", Applied Organometallic Chemistry, Vol. 8, p. 223-228, 1994.
10. Jennifer A. Wilkie and Janet G. Hering, " Adsorption of arsenic onto hydrous ferric oxide: effects of adsorbate/adsorbent ratios and co-occurring solutes", Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 107, p.97-110, 1996.
11. E. A. Woolson, "Fate of Arsenicals in Different Environmental Substrates", Environmental Health Perspectives, Vol. 19, p. 73-81, 1977.
12. Kang Xia, William Bleam and Philip A. Helmke, "Studies of the nature of binding sites of first row transition elements bound to aquatic and soil humic substances using X-ray absorption spectroscopy", Geochimica et Cosmochimica Acta, Vol. 61, No. 11, p. 2223-2235, 1997.
13. W. V. Gerasimowicz and D. M. Byler, "Carbon-13 CPMAS NMR and FTIR Spectroscopic Studies of Humic Acids", Soil Science, Vol. 139, No. 3, 1985.
14. W. M. Davis, C. L. Erickson, C. T. Johnston, J. J. Delfino and J. E. Porter, "Quantitative Fourier Transform Infrared Spectroscopic Investigation of Humic Substance Functional Group Composition", Chemosphere, Vol. 38, No. 12, p. 2913-2928, 1999.
15. Noam Gressel, Yossi Inbar, Arieh Singer and Yona Chen, "Chemical and Spectroscopic Properties of Leaf Litter and Decomposed Organic Matter in the Carmel Range, Israel", Soil Biol. Biochem., Vol. 27, No. 1, p. 23-31, 1995.
16. Nelson Belzile, Helen A. Joly and Hongbo Li, "Characterization of humic substances extracted from Canadian lake sediments", Can. J. Chem., Vol. 75, p.14-27, 1997.
17. Julieta A. Fereira, Otaciro R. Nascimento and Ladislau Martin-Neto, "Hydrophobic Interactions between Spin-Label 5-SASL and Humic Acid as Revealed by ESR Spectroscopy," Environ. Sci. Technol., Vol. 35, No. 4, p.761-765, 2001.
18. J. G. Sah, J. Y. Chen, "Study of the electrokinetic process on Cd and Pb spiked soils", Journal of Hazardous Materials, Vol. 58, p. 301-315, 1998.
19. Chris D. Cox, Matthew A. Shoesmith and Mriganka. M. Ghosh, "Electrokinetic Remediation of Mercury-Contaminated Soils Using Iodine/Iodide Lixiviant", Environ. Sci. Technol., Vol. 30, p. 1933-1938, 1996.
20. Alexandra B. Ribeiro and Joao T. Mexia, "A dynamic model for the electrokinetic removal of copper from a polluted soil", Journal of Hazardous Materials, Vol. 56, p. 257-271, 1997.
21. Yalcin B. Acar and Akram N. Alashawabkeh, "Principles of Electrokinetic Remediation", Environ. Sci. Technol., Vol. 27, No. 13, p. 2638-2647, 1993.
22. Sa V. Ho, P. Wayne Sheridan, Christopher J. Athmer, Michael A. Heitkamp, Joan M. Brackin, Deborah Webber and Philip H. Brodsky, "Integrated In Situ Soil Remediation Technology: the Lasagna Process", Environ. Sci. Technol., Vol. 29, No. 10, p. 2528-2534, 1995.
23. Shannon D., " "Lasagna process" field success increases DOE's interest", Environ. Sci. Technol., Vol. 29, No. 10, p.452 A, 1995.
24. Huang, Y.-J. and Wang, H. P., "Reduction of NO with CH4 Effected by Copper Oxide Clusters in the Chennels of ZSM-5", J. Phys. Chem. A, Vol. 103, p.6514, 1999.
25. Huang, Y.-J. and Wang, H. P.; Lee, J.-F., "NO Reduction on Cu-ZSM-5 Studied by EXAFS", Chemosphere, Vol. 39, p.1347, 1999.
26. Lin, K.-S. and Wang, H. P., "Shape selectivity of trace by-products for supercritical water oxidation of 2-chlorophenol effected by CuO/ZSM-48", Appl. Catal. B: Environ., Vol. 22, p. 261, 1999.
27. Lin, K.-S. and Wang, H. P., "Supercritical Water Oxidation of 2-Chlorophenol Catalyzed by Cu2+ Cations and Copper Oxide Clusters", Environ. Sci. Technol, Vol. 34, p. 4849-4854, 2000.
28. Lin, K.-S. and Wang, H. P., "Byproduct Shape Selectivity in Supercritical Water Oxidation of 2-Chlorophenol Effected by CuO/ZSM-5", Langmuir, Vol. 16, p. 2627, 2000.
29. Hung-Yi Chiou, Yu-Mei Hsueh, Kuen-Fu Liaw, Shang-Far Horng, Ming-His Chiang, Yeong-Shian Pu, Johnny Shinn-Nan Lin, Chun-Hsiung Huang and Chien- Jen Chen, "Incidence of Internal Cancers and Ingested Inorganic Arsenic: A Seven-Year Follow-up Study in Taiwan", Cancer Research, Vol. 55, p.1296-1300, March 15, 1995.
30. Chien-Jen Chen, Tsung-Li Kuo and Mei-Man Wu, "Arsenic and Cancers", Lancet, p.414-415, 1988.
31. Reinout Lageman, "Electroeclamation Applications in the Netherlands", Environ. Sci. Technol., Vol. 27, No. 13, p.2648-2650, 1993.
32. William R. Cullen and Kenneth J. Reimer, "Arsenic Speciation in the Environment", Chem. Rev., Vol. 89, p.713-764, 1989.
33. T. C. Hutchinson and K. M. Meema, "Lead, Mercury, Cadmium and Arsenic in the Environment", John Wilson & Sons Ltd, p.43-68, 1987.
34. U.S. Environmental Protection Agency, "Mercury and Arsenic Wastes: Removal, Recovery, Treatment, and Disposal", Noyes Data Corporation, p.60-69, 1992.
35. National Research Council, "Arsenic in drinking water", National Academy of Sciences, p.27-46, 1999.
36. Cerry, J. A., Shaikh, A. U., Tallman, D. E. and R. V. Nicholson, "Arsenic species as an indicator of redox conditions in groundwater", J. Hydrology, Vol. 43, p.373-392, 1979.
37. H. Xu, B. Allard and A. Grimvall, "Effects of Acidification and Natural Organic Materials on the Mobility of Arsenic in the Environment", Water, Air, Soil Pollution, Vol. 57-58, 269-278, 1991.
38. Willard R. Chappell, Charles O. Abernathy and C. Richard Cothern, "Arsenic exposure and health", Science and Technology Letters, Northwood, 1994
39. Chien- Jen Chen, "Blackfoot disease", Lancet, p.442, 1990.
40. Kenzaburo Tsuchiya, "Various Effects of Arsenic in Japan Depending on Type of Exposure", Environmental Health Perspectives, Vol. 19, p. 35-42, 1977.
41. Toshihide Tsuda, Eiji Yamamoto, Akria Babazono, Yoshio Mino, Yoshiki Kishi, Norio Kukanori, Tahanori Ogawa and Hideyasu Aoyama, "Comparisons of Survival Time Estimates for Niigata Prefecture (Japan) Residents Exposure to Ingested Arsenic", Applied Organometallic Chemistry, Vol. 8, p. 237-244, 1994.
42. Brown K. G., Chen C., "Significance of Exposure Assessment to Analysis of Cancer Risk from Inorganic Arsenic in Drinking Water in Taiwan", Risk Analysis, Vol. 15, No. 4, p.475-484, 1995.
43. F. J. Lu, "Arsenic as a Promoter in the Effect of Humic Substances on Plasma Prothrombin Tim in Vitro", Thrombosis Research, Vol. 58, p.537-541, 1990.
44. F. J. Lu and Y. S. Lee, "Humic acid: inhibitor of plasmin", The Science of Total Environment, Vol.114, p. 135-139, 1992.
45. Russell F. Christman and Egil T. Gjessing, "Aquatic and Terrestrial Humic Materials", Ann Arbor Science, 1983.
46. Keith E. Dennett, Appiah Admirtharajah, Anne Studstill, Thomas F. Moran and Joseph P. Gould, "Humic Substance Removal and Minimization of Trihalomethanes by Ferric Chloride Coagulation", AWWA Research Foundation, 1995.
47. Hsiao-wen Chen, Michelle M. Frey, Dennis Clifford, Laurie S. McNeill and Marc Edwards, "Arsenic treatment considerations", Journal AWWA, Vol. 91, 74-85, 1999.
48. T. Viraraghavan, K. S. Subramanian and J. A. Aruldoss, "Arsenic In Drinking Water-Problems And Solutions", Wat. Sci. Tech., Vol. 40, No. 2, 69-76, 1999.
49. Paul D. Kuhlmeier and Steven P. Sherwood, "Treatability of inorganic arsenic and organoarsenicals in groundwater", Water Environment Research, Vol. 68, No. 5, 946-951, 1996.
50. F. G. A. Vagliasindi and Mark M. Benjamin, "Arsenic Removal In Fresh And Nom-Preloaded Ion Exchange Packed Bed Adsorption Reactors", Wat. Sci. Tech, Vol. 38, No. 6, 337-343, 1998.
51. Matthew L. Pierce and Carleton B. Moore, "Adsorption of Arsenite on Amorphous Iron Hydroxide from Dilute Aqueous Solution", Environmental Science & Technology, Vol. 14, No. 2, 214-216, 1980.
52. Andrea L. Foster, Gordon E. Brown Jr., Tracy N. Tingle and George A. Parks, "Quantitative arsenic speciation in mine tailings using X-ray absorption spectroscopy", American Mineralogist, Vol. 83, 553-568, 1998.
53. Klaus P. Raven, Amita Jain and Richard H. Loeppert, "Arsenite and Arsenate Adsorption on Ferrihydrite: Kinetics, Equilibrium, and Adsorption Envelopes", Environmental Science & Technology, Vol. 32, No. 3, 344-349, 1998.
54. G. A. Waychunas, B. A. Rea, C. C. Fuller and J. A. Davis, "Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate", Geochimica et Cosmochimica Acta, Vol. 57, 2251-2269, 1993.
55. Christopher C. Fuller, James A, Davis and Glenn A. Waychunas, "Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation", Geochimica et Cosmochimica Acta, Vol. 57, 2271-2282, 1993.
56. Alain Manceau, "The mechanism of anion adsorption on iron oxides: Evidence for the bonding of arsenate tetrahedra on free Fe (O, OH) 6 edges", Geochimica et Cosmochimica Acta, Vol. 59, 3647-3653, 1995.
57. Glenn A. Waychunas, James A, Davis and Christopher C. Fuller, " Geometry of sorbed arsenate on ferrihydrite and crystalline FeOOH: Re-evaluation of EXAFS results and topological factors in predicting sorbate geometry, and evidence for monodentate complexes", Geochimica et Cosmochimica Acta, Vol. 59, 3655-3661, 1995.
58. Scott E. Fendorf, Gerry M. Lamble, Michael G. Stapleton, Michael J. Kelley and Donald L. Sparks, "Mechanism of Chromium (Ⅲ) Sorption on Silica. 1. Cr (Ⅲ) Surface Structure Derived by Extended X-ray Absorption Fine Structure Spectroscopy", Environmental Science & Technology, Vol. 28, No. 2, 284-289, 1994.
59. P. Diehl, E. Fluck, H. Gunther, R. Kosfeld and J. Seelig, "Solid-State NMR Ⅱ: Inorganic Matter", Springer-Verlag Berlin Heidelberg, p. 18, 1994.
60. Emmanuel Doelsch, William E. E. Stone, Sabine Petit, Armand Masion, Jerome Rose, Jean-Yves Bottero and Daniel Nahon, "Speciation and Crystal Chemistry of Fe(Ⅲ) Chloride Hydrolyzed in the Presence of SiO4 Ligands. 2. Characterization of Si-Fe Aggregates by FTIR and 29Si Solid-State NMR", Langmuir, Vol. 17, p. 1399-1405, 2001.
61. Hideki Maekawa and Toshio Yokokawa, "Effects of temperature on silicate melt structure: a high temperature 29Si NMR study of Na2Si2O5", Geochimica et Cosmochimica Acta, Vol. 61, No. 13, p. 2569-2575, 1997.
62. Raja A. Jadhav and Liang-Shih Fan, "Capture of Gas-Phase Arsenic Oxide by Lime: Kinetic and Mechanistic Studies", Environmental Science & Technology, Vol. 35, No. 4, p.794-799, 2001.
63. Kang Xia, William Bleam and Philip A. Helmke, "Studies of the nature of Cu2- and Pb2+ binding sites in soil humic substances using X-ray absorption spectroscopy", Geochimica et Cosmochimica Acta, Vol. 61, No. 11, p. 2211-2221, 1997.
64. J. Hamed, Y. B. Acar and R. J. Gale, "Pb(Ⅱ) removal from kaolinite by electrokinetic", J. Geotech. Eng., 117, p.241-271, 1991.
65. Brian E. Reed, Associate Member, ASCE, Mitchell T. Berg, John C. Thompson and Jarrod H. Harfield, "Chemical Conditioning of Electrode Reservoirs during Electrokinetic Soil Flushing of Pb-Contaminated Silt Loam", Journal of Environmental Engineering, p. 805-815, 1995.
66. F. Albert Cotton and Geoffrey Wilkinson, "Advanced Inorganic Chemistry", p.401, 1988.
67. M. May, M. Asomoza, T. Lopez and R. Gomez, "Precursor Aluminum Effect in the Synthesis of Sol-Gel Si-Al Catalysts: FTIR and NMR Characterization", Chem. Mater., Vol. 9, p. 2395-2399, 1997.
68. Claus J. H. Jacobsen, Claus Madsen, Ton V. W. Janssens, Hans J. Jackobsen and Jorgen Skibsted, "Zeolites by confined space synthesis-characterization of the acid sites in nanosized ZSM-5 ammonia desorption and 27Al/29Si-MAS NMR spectroscopy", Microporous and Mesoporous Materials, Vol. 39, p.393-401, 2000.
69. M. Muller, G. Harvey and R. Prins, "Quantitative multinuclear MAS NMR studies of zeolites", Microporous and Mesoporous Materials, Vol. 34, p.281-290, 2000.