臺灣博碩士論文加值系統

本研究將定量Benz(a)anthracene（B(a)A）添加在兩種介質（PTFE濾紙及含拜香燃煙PTFE濾紙），然後置於照光實驗腔，分別接受紫外線燈、普通型螢光燈及三波長型螢光燈三種等燈源之紫外線輻照，各自之輻照強度及光譜使用UV/VIS spectroradiometer測量，照光時間分別為0分鐘、30分鐘、60分鐘、90分鐘、120分鐘、150分鐘與180分鐘，照光後萃取，以HPLC定量殘留之B(a)A，用以檢驗輻照強度及照光時間對B(a)A的影響。
紫外線燈、普通型螢光燈及三波長螢光燈的總紫外線輻照強度分別為3909.420mw/m2、13.85 mw/m2、5.02 mw/m2；其中UVA（315-400nm）輻照強度分別為1309.431mw/m2、13.85 mw/m2、5.02 mw/m2。
B(a)A在PTFE濾紙上受紫外線燈與普通型螢光燈照射後，在觀察的照光時間內呈現明顯的減量，其濃度變化與照光時間的關係為一級反應，兩者相關的判定係數，R2值分別為0.9757和0.8988，反應速率常數（k值）為0.0085min-1和0.0004min-1，至於B(a)A在含拜香燃煙PTFE濾紙上受紫外線燈與螢光燈照射後，濃度變化與照光時間兩者關連的判定係數，R2值為0.5558和0.0225，反應速率常數（k值）降為0.0005min-1和0.00004min-1。再者，B(a)A降解速率常數（k值）分別與總輻照強度、UVA輻照強度的判定係數R2為0.9861與0.964。
總而言之B(a)A接受人工紫外線之輻照後會降解。其光降解速率因B(a)A所處介質不同而異，而且與輻照強度及輻照時間關係密切。

This study attempted to determine conditions influencing the photo-degradation of Benz(a)anthracene (B(a)A) spiked onto the PTFE membrane filter coated with or with no incense smoke. Samples were placed in an exposure chamber equipped with an ultraviolet (UV) lamp, a daylight fluorescence lamp or a three-band fluorescence lamp as the source of UV radiation to degrade the spiked B(a)A. Spectrum and irradiance of light were measured using the UV/VIS spectroradiometer. Samples were illuminated for 0 minute, 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes and 180 minutes prior to extraction with acetonitrile and for HPLC analysis. A series of blank tests also were tested parallel with the samples in similar UV radiation.
The total UV irradiance from the UV lamp, the daylight fluorescence lamp and the three-band fluorescence lamp were 3909.420 mw/m2, 13.85 mw/m2, 5.02 mw/m2, respectively, and in which UVA (315-400nm) accounted for 1309.431 mw/m2, 13.85 mw/m2 and 5.02 mw/m2, respectively.
Following the pseudo-first order reaction, the UV lamp and the daylight fluorescence lamp demonstrated a notable decrease in the concentration of B(a)A on PTFE filter, with the coefficients of determination (R2) of 0.9757 and 0.8988, and the degradation rates (k value ) of -0.0085min-1 and -0.0004min-1, respectively. In contrast, the R2s decreased to 0.5558 and 0.0225 and the k value dropped to -0.0005min-1 and -0.00004min-1 when B(a)A on the PTFE filter was coated with incense smoke. Furthermore, the R2s between k value of B(a)A and total UV irradiance and UVA irradiance were 0.986 and 0.964, respectively.
This study has demonstrated that B(a)A is degradable in the man-made UV radiation. The photodegradation rates happened to be dependent on the irradiance intensity and illumination time of the lamps and the nature of filters on which B(a)A is deposited.

目 錄
中文摘要Ⅰ
英文摘要Ⅲ
目 錄Ⅴ
表 列Ⅷ
圖 列Ⅸ
附 錄 列ⅩⅠ
第一章 緒論1
1.1背景1
1.2研究目的3
第二章 文獻探討4
2.1多環芳香烴化合物4
2.1.1定義4
2.1.2來源及存在環境4
2.1.3基本特性5
2.1.3.1物理性質5
2.1.3.2 化學特性7
2.2多環芳香烴之生物特性8
2.3 PAHs之光降解因子9
2.4 PAHs降解機制13
2.5PAHs光降解產物及毒性13
2.6螢光燈性質16
第三章 材料與方法17
3.1儀器設備與材料17
3.2藥品試劑及其他耗材19
3.3研究架構20
3.4溶液的配製20
3.4.1 儲備溶液21
3.4.2 內標溶液配製21
3.4.3 檢量溶液之配製21
3.5拜香燃煙之產生與採集21
3.5.1 燃燒室之構造22
3.5.2 燃燒拜香用支撐架之設備22
3.6照光試驗室之構造22
3.7人工紫外線之來源23
3.8普通型螢光燈、三波長螢光燈及紫外線燈光譜之分析23
3.8.1 UV/VIS-spectroradiometer原理23
3.8.2 量測普通型螢光燈和三波長型螢光燈之紫外線光譜23
3.8.3 量測紫外線燈之紫外線光譜24
3.9粒狀物質（以拜香燃煙為代表）採樣程序24
3.10樣本重量分析25
3.11真實B(a)A的添加25
3.12照光程序26
3.13儀器偵測極限（Instrument Detection Limit）26
3.14化學分析27
3.14.1檢量線之製作27
3.14.2樣本前處理27
3.14.3樣本分析27
第四章 結果30
4.1 檢量線與HPLC結果30
4.2 紫外線光譜分析之結果30
4.2.1螢光燈之紫外線光譜分析結果30
4.2.2紫外線燈之紫外線光譜分析結果31
4.3 B(a)A在PTFE濾紙上受人工紫外線輻照之降解情形32
4.3.1 B(a)A受紫外線燈輻照後之降解情形32
4.3.2 B(a)A受普通型螢光燈輻照後之降解情形33
4.3.3 B(a)A受三波長螢光燈輻照之降解情形33
4.4 B(a)A在含拜香燃煙之PTFE濾紙受人工紫外線輻照之降解情形34
4.4.1 B(a)A受紫外線燈輻照之降解情形34
4.4.2 B(a)A受普通型螢光燈輻照之降解情形34
4.5 比較兩介質（PTFE濾紙或含拜香燃煙PTFE濾紙）上B(a)A受人工紫外線輻照之降解情形35
4.5.1 B(a)A受紫外線燈照射之降解情形35
4.5.2 B(a)A受普通型螢光燈照射之降解情形35
4.6B(a)A降解與人工紫外線強度之關係35
4.7 溫度變化對B(a)A降解之影響36
4.8B(a)A降解產物之追蹤36
4.8.1 HPLC-UV detector 分析37
4.8.2 GC-MS 分析37
第五章 討論38
5.1拜香燃煙之採樣38
5.2 照光實驗之結果討論38
5.3 B(a)A 降解產物之追蹤40
第六章 結論42
第七章 參考文獻43
表 列
表 一 B(a)A之HPLC分析條件 51
表 二 氣相層析質譜分析儀（GC-MS）分析條件 52
表 三 螢光燈之紫外線輻照分佈53
表 四 普通型螢光燈沒有石英玻璃隔絕之紫外線輻照分佈54
表 五 普通型螢光燈有石英玻璃隔絕之紫外線輻照分佈55
表 六 三波長型螢光燈沒有石英玻璃隔絕之紫外線輻照分佈56
表 七 三波長型螢光燈有石英玻璃隔絕之紫外線輻照分佈57
表 八 普通型螢光燈包裹一層絕熱紙且有石英玻璃隔絕之紫外線輻照 分佈58
表 九 紫外線燈沒有石英玻璃隔絕之紫外線輻照分佈59
表 十 紫外線燈有石英玻璃隔絕之紫外線輻照分佈 60
表 十一 紫外線燈包裹一層絕熱紙且有石英玻璃隔絕之紫外線輻照分佈61
表 十二 三種燈源的紫外線光譜分析之結果總整理62
圖 列
圖一 研究架構63
圖二 燃燒室構造示意圖64
圖三 普通型螢光燈及三波長螢光燈照光實驗示意圖65
圖四 紫外線燈照光實驗示意圖66
圖五 採樣流程圖67
圖六 照光程序之流程68
圖七 樣品前處理流程69
圖八 Benz(a)anthracene之檢量線70
圖九 Benz(a)anthracene 標準品液相層析儀圖譜71
圖十 普通型螢光燈沒有石英玻璃隔絕之紫外線輻照分佈圖譜72
圖十一 普通型螢光燈有石英玻璃隔絕之紫外線輻照分佈圖譜73
圖十二 三波長型螢光燈沒有石英玻璃隔絕之紫外線輻照分佈圖譜74
圖十三 三波長型螢光燈有石英玻璃隔絕之紫外線輻照分佈圖譜75
圖十四 普通型螢光燈包裹一層絕熱紙且有石英玻璃隔絕之紫外線輻照分佈圖譜76
圖十五 紫外線燈沒有石英玻璃隔絕之紫外線輻照分佈圖譜77
圖十六 紫外線燈有石英玻璃隔絕之紫外線輻照分佈圖譜78
圖十七 紫外線燈包裹一層絕熱紙且有石英玻璃隔絕之紫外線輻照分佈圖譜79
圖十八 B(a)A受紫外線燈照射後濃度之變化圖80
圖十九 B(a)A受紫外線燈照射後之一級反應變化圖80
圖二十 B(a)A受普通型螢光燈照射後濃度之變化圖81
圖二十一 B(a)A受普通型螢光燈照射後之一級反應變化圖81
圖二十二 B(a)A受三波長型螢光燈照射後濃度變化圖82
圖二十三 含拜香燃煙之PTFE濾紙上B(a)A受紫外燈照射之一級反應圖82
圖二十四 含拜香燃煙之PTFE濾紙上B(a)A受普通型螢光燈照射之一級反應圖83
圖二十五 B(a)A在兩種不同介質受紫外燈照射之一級反應圖83
圖二十六 B(a)A在兩種不同介質受普通型螢光燈紫外燈照射之一級反應圖84
圖二十七 B(a)A受不同紫外線輻照強度照射之濃度變化圖84
圖二十八 B(a)A受不同紫外線輻照強度照射之一級反應變化圖85
圖二十九 K值與總UV輻照強度之關係85
圖三十 K值與UVA總輻照強度之關係86
圖三十一 ln(Ct/C0)對每個時間點之溫度的倒數（°K-1）作圖87
圖三十二 B(a)A未照光之HPLC-UV分析圖譜88
圖三十三 B(a)A照光180分鐘之HPLC-UV分析圖譜88
圖三十四 B(a)A之GC-MS分析圖譜及荷質比圖89
圖三十五 內標（p-terphenyl）之GC-MS分析圖譜及荷質比圖90
圖三十六 低濃度B(a)A未照光之GC-MS分析圖譜91
圖三十七 低濃度B(a)A照光30分GC-MS分析圖譜91
圖三十八 低濃度B(a)A照光90分鐘GC-MS分析圖譜92
圖三十九 B(a)A照光180分鐘之GC-MS分析圖譜92
圖四十 高濃度組B(a)A照光0分鐘之GC-MS分析圖譜93
圖四十一 高濃度組B(a)A照光180分鐘之GC-MS分析圖譜93
附 錄
附錄一 16種多環芳香烴化合物之特性94
附錄二 Proposed Toxic Equivalency Factors (TEFs) for individual PAHs95
附錄三 16種多環芳香烴化合物之結構圖96
附錄四 石英樣品瓶之示意圖97

1. World Health Organization, Air Quality Guildeline for Europe, WHO regional pub. European series NO.23, Denmark 1987：105-126
2. Petry T., Schmid P. and Schlatter C. (1996) The use of toxic equivalency factors in assessing occupation and environmental health risk associated with exposure to airborne mixture of polycyclic aromatic hydrocarbons (PAHs), Chemosphere 32:639-648
3. Josephson J. (1984) Polynuclear aromatic hydrocarbons, Environ Sci & Technol 18:93A-95A
4. Raiyani C.V., Jani J.P., Desai N.M., Shah S.H., Shan P.G., Kashyap S.K. (1993) Assessment of indoor exposure to polycyclic aromatic hydrocarbons for urban poor using various types of cooking fules, Bull Environ Contam Toxicol 50:757-763
5. Nordholm L., Espensen I. M., Jensen H.S., Holst E. (1986) Polycyclic aromatic hydrocarbons in smokehouses, Scand Work Environ Health 12:614-618
6. Sinks G.D., Schultz T.W., Hunter R.S. (1997) UVb-induced toxicity of PAHs: effects of substituents and heteroatom substitution, Bull Environ Contam Toxicol 59:1-8
7. Lofroth G., Stensman C., Margareta B.S. (1991) Indoor sources of mutagenic aerosols particulates matter: smoking, cooking and incense burning, Mutation Research 261:21-28
8. 曾國城1996，拜香原料燃燒產生之多還芳香烴化合物，國立台灣大學公共衛生研究所碩士論文
9. Lin J.M., Lee J.K. （1997）Vapor phase and particulate-bound polycyclic aromatic hydrocarbons in the smoke of mosquito coil, Bull Environ Control Toxicol 59(6):868-874
10. 姜泰安1997，烹飪油煙之至突變異性與致癌物分析及預防暴露之研究，高雄醫學院醫學研究所博士論文，p104
11. World Health Organization ，Air Quality Guildeline for Europe，WHO regional pub. European series NO.23，Denmark 1987：91-104
12. Takeda N., Teranishi K.（1986）Effects of environmental conditions on polycyclic aromatic hydrocarbons and mutagenicity of airborne particulate matter, Bull Environ Contam Toxicol 36:685-692
13. Nielsen T., Jorgensen H.E., Larsen J.C., Poulsen M. (1996) City air pollution of polycylic aromatic hydrocarbons and other mutagens: occurrence , sources and health effects, The Science of total Environment 189/190:41-49
14. Chen C.C., Lee H. (1996) Genotoxicity and DNA adduct formation of incense smoke condensates : comparison with environmental tobacco smoke condensates, Mutation Reasearch 367:105-114
15. Kamens R.M., Hua F.Z., Yao Y., Chen D., Chen S., Vartiainen M. (1994) A methodology for modeling the formation and decay of nitro-PAH in the atmosphere, Chemosphere 28:1623-1632
16. Moller M., Hagen I., Ramadahl T. (1985) Mutagenicity of polycyclic aromatic compounds (PAC) identified in source emissions and ambient air, Mutation Research 157:149-156
17. Schoental R., Gibbard S. （1967） Carcinogens in Chinese Incense Smoke, Nature 216:612
18. Chuang J.C., Cao S.R., Xian Y.L., Harris D.B., Mumford J.L. (1992) Chemical characterization of indoor air of homes from communes in Xung Wei , China , with high lung cancer mortality rate, Atmospheric Environment, 26A:2193-2201
19. Helmig D., Arey J., Atkinson R., Harger W., Mcelroy P.A.. (1992) Products of the OH radical-initiated gas-phase reaction of fluorene in the presence of NOx, Atmosphere Environment 26A:1735-1745
20. Kwok E.S., Harger W.P., Arey J., Atkinson R. (1994) Reactions of gas-phase Phenanthrene under simulated atmospheric conditions, Environ Sci & Technol 28:521-527
21. Jang M., McDow S.R. (1995) Benz(a)anthracene photodegradation in the presence of known organic constituents of atmospheric aerosols, Environ Sci & Technol 29:2654-2660
22. Kamens R.M., Perry J.M., Saucy D.A., Bell D.A ., Newton D.L., Brand B. (1985) Factors which influence polycyclic aromatic hydrocarbons decomposition on wood smoke particles, Environment International 11:131-136
23. Kamens R.M., Guo Z., Fulcher J.N., Bell D.A. (1988) Influence of humidity, sunlight, and temperature on the daytime decay of polyaromatic hydrocarbons on atmosphere soot particles, Environ Sci & Technol 22:103-108
24. McDow S.R.., Sun Q.R., Vartiainen M., Hong Y.L., Fister T., Yau R.Q., Kamens R.M. (1994) Effect of composition and state of organic compounds on polycyclic aromatic hydrocarbon decay in atmospheric aerosols, Environ Sci & Technol 28:2147-2153
25. Odum J.R., McDow S.R and Kamens R.M. (1994) Mechanistic and kinetic studies of the photodegradation of Benz(a)anthracene in the presence of methoxyphenols, Environ Sci & Technol 28:1285-1290
26. McDow S.R., Vartiainen M., Sun Q.R., Hong Y., Yao Y., Kamens R.M. (1995) Combustion aerosol water content and its effect on polycyclic aromatic hydrocarbon reactivity, Atmospheric Environment 29:791-797
27. 王俊龍 1997，拜香燃煙中多環芳香烴化合物組成受螢光燈照射之影響，國立台灣大學公共衛生研究所碩士論文
28. Beak S.O.（1991）A review of atmospheric polycyclic aromatic hydrocarbons sources, fate, and behavior, Water, Air, and Soil Pollution 60:279-300
29. Moriske H.J., Drews M., Ebert G., Menk G., Scheller C., Mchondube M., Konieczny L. (1996) Indoor air pollution by different heating system:coal burning, open fireplace and central heating, Toxicology Letters 88:349-354
30. 李建坤1996，拜香及蚊香燃燒產生之多環芳香烴化合物，國立台灣大學公共衛生研究所碩士論文
31. Lee M.L., Novotny M.V., Bartle K.D. (1981) Analytical Chemistry of Polycyclic Aromatic Hydrocarbons, Academic Press, New York
32. Hall M. and Grover P.L. (1990) Polycyclic aromatic hydrocarbons: chemical carcinogenesis and mutagenesis Ⅰ, Springer-Verlag press, Berlin , Heidelberg , New York, 327-359
33. Arfsten D.P., Schaeffer D.J., Mulveny D.C. (1996) The effect of near ultraviolet radiation on the toxic effects of polycyclic aromatic hydrocarbons in animals and plants: Review, Ecotoxicology and Environmental Safety 33:1-24
34. Torben N. (1988) The decay of Benzo(a)pyrene and Cyclopenteno(cd)pyrene in the atmosphere , Atmospheric Environment 22:2249-2254
35. Cimberle M.R. , Bottino P., Valerio F. (1983) Decomposition of Benzo(a)pyrene deposited on glass fiber filters and exposed to sunlight, Chemosphere 12:317-324
36. Tancell P.J., Rhead M.M., Pemberton R.D. and Braven J. (1995) Survival of polycyclic aromatic hydrocarbons during diesel combustion, Environ Sci & Technol 29:2871-2876
37. Kamens R.M, Fulcher J.N. and Guo Z. (1986) Effect of temperature on wood soot PAH decay in atmospheres with sunlight and low NOx , Atmospheric Environmet 20:1579-1587
38. Bell D.A. and Kamens R.M. (1986) Photodegradation of wood smoke mutagens under low NOx conditions, Atmospheric Environment 20:317-321
39. Lindkog A. , Brorstrom-Lunden E. and Sjodin A. (1985) Transformation of reaction PAH on particles by exposure to oxidized nitrogen compounds and ozone, Environment International 11:125-130
40. Vaeck L.V. and Cauwenberghe K.V. (1984) Conversion of polycyclic aromatic hydrocarbons on diesel particulate matter upon exposure to ppm levels of ozone, Atmospheric Environment 18:323-328
41. Peltonen K. and Kuljukka T. (1995) Air sampling and analysis of polycyclic aromatic hydrocarbons, Journal of Chromatography A 710:93-108
42. Inscoe M.N. (1964) Photochemical changes in thin layer chromatograms of polycyclic aromatic hydrocarbons, Aanlytical Chemistry 36:2505-2506
43. Korfmacher W.A (1980) Oxidative transformation of polycyclic aromatic hydrocarbons adsorbed on coal fly ash, Science 207:763-765
44. Behymer T.D. , Hites R.A. (1988) Photolysis of polycyclic aromatic hydrocarbons adsorbed on fly ash, Environ Sci & Technol 22:1311-1319
45. Korfmacher W.A., Wehry E.L., Mamantov G., Natusch D.F.S. (1980) Resistance to photochemical decomposition of polycyclic aromatic hydrocarbons vapor-adsorbed on coal fly ash, Environ Sci & Technol 14:1094-1099
46. Butler J.D. and Crossley P. (1980) Reactivity of polycyclic aromatic hydrocarbons adsorbed on soot particles, Atmospheric Environment 15:91-94
47. Behymer T.D. and Hites R.A. (1985) Photolysis of polycyclic aromatic hydrocarbons adsorbed on simulated atmospheric particulates, Environ Sci & Technol 19:1004-1006
48. Thomas J.F., Mukai M., Tebbens B.D. (1968) Fate of airborne Benzo(a)pyrene, Environ Sci & Technol 2:33-39
49. Leslle E.A., Geoffrey R.N. (1991) Analysis of condensates from wood smoke:components derived from polysaccharides and lignins, Environ Sci & Technol 25:1133-1137
50. Sweetman J.A., Zielinska B., Atkinson R.T., Ramdahl A. (1986) A possible formation pathway for 2-nitrofluoranthene observed in ambient particulate organic matter, Atmospheric Environment 20:235-238
51. Eisenberg W.C., Taylor K. , Murray R. W. (1984) Production of singlet delta oxygen by atmospheric pollutants, Carcinogenic 5:1095-1096
52. Ramdahl T. (1983) Polycyclic aromatic ketones in environmental samples, Environ Sci & Technol 17:666-670
53. Kamens R.M., Karam H., Guo J., Perry J.M., Stockburger L. (1989) The behavior of oxygenated polycyclic aromatic hydrocarbons on atmosphere soot particles, Environ Sci & Technol 23 :801-806
54. Payne J.R., Philips C.R. (1985) Photochemistry of petroleum in water, Environ Sci & Technol 19 :569-579
55. Jang M., McDow S.R. (1997) Product of Benz(a)anthracene photodegradation in the presence of known organic constituents of atmospheric aerosols, Environ Sci & Technol 31:1046-1053
56. Chen J.W., Kong L.R., Zhu C.M., Huang Q.G., Wang L.S. (1996) Correlation between photolysis rate constants of polycyclic aromatic hydrocarbons and frontier molecular orbital energy, Chemosphere 33:1143-1150
57. Fernandez M., L'Haridon J. (1992) Influence of lightling conditions on toxicity and genotoxicity of various PAH in the newt in vivo, Mutation Research 298:31-41
58. Pucknat A.W. (1981) Health Impact of Polycyclic Aromatic Hydrocarbons , Park Ridge, New Jersey, USA, p102-103
59. 洪長業1987，螢光燈的發展趨勢，照明學刊4（3）：74-86
60. Maxwell K. J., Elwood J M. (1983) UV radiation from fluorescence lights, The Lancet 3:579
61. National Institute for Occupational Safety and Health (1994), NIOSH Manual of Analytical Methods (4th Ed.), Vol 3, Method 5506
62. 張展銓1998，螢光燈照射下多環芳香烴化合物之變化，國立台灣大學環境衛生研究所碩士論文
63. Mumford J.L., Chapman R.S., Harris D.B., He X.Z., Gao S.R., Xian Y.L., and Li X.M. (1989) Indoor air exposure to coal and wood combustion emissions associated with a high lung cancer rate in Xuan Wei China, Environment international 15:315-320,
64. Lin J.M. , and Lee J.K (1998) Vaporous and particulate-bound polycyclic aromatic hydrocarbons in Chinese incense smoke, Toxicological and Environmental Chemistry 67:105-113
65. Fox M.A., Olive S., (1979) Photooxidation of Anthracene on atmospheric particulate matter, Science 205:582-583