臺灣博碩士論文加值系統

多環芳香烴碳氫化合物是環境中分佈廣泛的污染物質，主要是由石化物或有機物質在缺氧狀態下，因不完全燃燒所產生之熱分解或熱合成的反應產物。由於具有致癌性與致畸性，且因結構穩定，容易累積於環境之中，因此對人類及生態環境有相當的危害性。
研究中探討了柴油引擎粒狀物中PAHs的含量，首先以dichloromethane為溶劑，以3-5 cycles/hr的速率索氏萃取二十小時，萃取液經過減壓濃縮、置換溶劑後流經矽膠管柱淨化，將所收集的沖提液以吹氮的方式濃縮至適當體積，並添加內標準品，進行後續之GC/MS檢測。另一部份，則是探討以微波輔助頂空液相微萃取分析水樣品中PAHs之可行性，萃取溶劑使用octane，所得最佳化參數為溶劑懸掛位置距冷凝管口底部0.5 cm，萃取溫度90 ℃，冷凝溫度10 ºC，微波功率210w，吸附時間18分鐘，不添加鹽類。萃取完成之後，將萃取液滴直接注入GC/MS進行檢測。
柴油引擎排放粒狀物樣品的分析，以標準參考物質NIST SRM1649a來確認整體分析流程，回收率介於65-128%之間。方法偵側極限預估值則為1.90-22.01 ppb。經由分析所得數據發現，柴油引擎排放粒狀物樣品中所偵測到的PAHs，以naphthalene、2-methylnaphthalene、acenaphthylene、acenaphthene、flourene、phenanthrene、anthracene、flouranthene、pyrene、benz(a)anthracene、chrysene、benzo(b)fluoranthene、benzo(k)fluoranthene、benzo(e)pyrene在樣品中出現的頻率較高。而微波輔助頂空液相微萃取分析水樣品中PAHs之方法線性範圍介於0.005~20 ppb之間，相關係數均大於0.99，偵測極限則介於0.0010~0.0807 ppb。並與傳統水浴加熱作一比較，發現四環以上之PAHs以微波輔助加熱能達到更優越的萃取效果，最好可達到水浴加熱的1.60倍。因此，微波輔助頂空液相微萃取是一個快速、方便並可應用於環境中水質樣品檢測的技術

Polycyclic aromatic hydrocarbons(PAHs) are widespread environmental pollutants,which are formed during the incomplete combustion of organic material.Because of the suspected mutagenic and carcinogenic behaviors for many PAHs,hence, is concern for human health and environmental quality.
The thesis is devided into two parts.Part I:Analysis of polycyclic aromatic hydrocarbons in diesel engine exhaust and ambient air particles. Part II:Determination of polycyclic aromatic hydrocarbons in aqueous samples with microwave-assisted headspace liquid phase micro-extraction completed with gas chromatography/mass detector method.
In the study of part I, the amounts of PAHs in diesel engine emission exhaust and ambient air samples was analyzed by the Taiwan EPA method NIEA M183.00C.Standard urban dust material SRM 1649a was used for the validation of extraction conditions and the recovery range from 65-128%. The method detection limit obtained were between 1.90-22.01ppb.The correlation coefficients exceeded 0.996 for the linear dynamic range from 0.05-20ppm for all analytes.The diesel engine exhaust collected from Automotive Reaserch and Testing center in central Taiwan and ambient air samples collected from Kaohsiung city.
In part II,sample preparation of PAHs in aqueous samples by MA-HS-LPME has been described.Experimental results indicated that the proposed MA-HS-LPME technique attained the best extraction efficiency under the optimized conditions, i.e.,use octane as extraction solvent and irradiation of extraction solution (50 ml aqueous sample with no addition of salt) under 210W microwave power for 18 min at 90 ℃ with the cooling system maintain at 10 ℃.The detection was linear at 0.005-20 ppb with correlation coefficient exceeded 0.99 . The detection limit obtained were between 0.0010-0.0807 ppb. Water samples collected from a tank in National Kaohsiung Normal University campus were analysed using the optimised conditions.

中文摘要----------------------------------------------------Ⅰ
英文摘要----------------------------------------------------Ⅱ
目錄--------------------------------------------------------Ⅲ
圖次--------------------------------------------------------V
表次--------------------------------------------------------VI
第一章 緒論-------------------------------------------------1
1-1 前言-------------------------------------------------1
1-2 多環芳香烴化合物（PAHs）---------------------------------2
1-2-1 PAHs簡介---------------------------------------------2
1-2-2 PAHs之研究源起---------------------------------------4
1-2-3 PAHs之特性------------------------------------------4
1-2-4 環境中PAHs之分佈情況----------------------------------7

1-3 柴油引擎排氣粒狀物--------------------------------------7
1-3-1 柴油引擎之污染排放特徵---------------------------------8
1-3-2 柴油引擎車輛排氣粒狀物與人體健康之關係-------------------9

1-4 微波-------------------------------------------------9
1-4-1 微波發展簡介------------------------------------------9
1-4-2 微波加熱原理------------------------------------------10
1-4-3 微波特性----------------------------------------------12
1-4-4 影響微波的因素-----------------------------------------14
1-4-5 微波輔助萃取原理---------------------------------------15
1-4-6 微波加熱法與傳統加熱法的比較-----------------------------15
1-4-7 微波裝置圖 ---------------------------------------------16

1-5 樣品前處理方法--------------------------------------------19
1-6 研究目的-------------------------------------------------25
第二章 柴油引擎車輛排氣粒狀物樣品中PAHs之分析--------------------26
2-1 PAHs分析流程---------------------------------------------26
2-2 試劑與標準品 ---------------------------------------------27
2-3 儀器設備及器材--------------------------------------------28
2-4 分析儀器-------------------------------------------------29
2-5 分析步驟-------------------------------------------------33
2-6 數據處理-------------------------------------------------33
2-7 結果與討論------------------------------------------------34
2-7-1 PAHs氣相層析-質譜儀檢量線與儀器偵測極限--------------------34
2-7-2 PAHs各分析步驟回收率試驗---------------------------------36
2-7-3 PAHs標準參考樣品分析結果---------------------------------38
2-7-4 柴油引擎排放粒狀物樣品PAHs之分析--------------------------41
2-7-5 週界空氣樣品Ambient Air Sample之PAHs分析結果-------------52
2-7-6 週界空氣粒狀物樣品分析-----------------------------------58
2-7-7 方法偵測極限--------------------------------------------59
第三章 微波輔助頂空液相微萃取分析水樣品中PAHs---------------------62
3-1 實驗流程-------------------------------------------------62
3-2 藥品-------------------------------------------------63
3-3 儀器設備及器材--------------------------------------------64
3-3-1 實驗儀器裝置圖------------------------------------------64

3-4 分析儀器------------------------------------------------65
3-5 實驗過程------------------------------------------------66
3-6 結果與討論-----------------------------------------------69
3-6-1 氣相層析方法的建立--------------------------------------70
3-6-2 頂空液相微萃取分析水中16種PAHs萃取參數的探討---------------73
3-6-3 比較微波輔助加熱萃取和傳統水浴加熱萃取的差異性--------------82
3-6-4 微波輔助加熱頂空液相微萃取方法的建立 ---------------------85
3-6-5 微波輔助加熱頂空液相微萃取分析水樣品PAHs之濃縮倍率----------86
3-6-6 真實樣品的檢測------------------------------------------87
3-6-7 與其他文獻之比較----------------------------------------89
第四章 結論-------------------------------------------------91
參考文獻------------------------------------------------92
附 錄 一------------------------------------------------96
附 錄 二------------------------------------------------101
附 錄 三------------------------------------------------106

1.王正雄，1999，淺談「環境荷爾蒙」-干擾動物內分泌之化學物質，環境檢驗通訊雜誌，24。
2.Zandere, M., 1985. Physical and Chemical Properties of Polycyclic Aromatic Hydrocarbons. Marcel Dekker Inc.
3.賴臆雯，2000，大氣塵粒中多環芳香烴粒徑分布特性之研究，國立清華大學碩士論文。
4.Pott, P., 1775. “Chirurgical Observations Relative to the Cataract, the Polypus of the Nose, the Cancer of the Scrotum, the Different Kinds of Ruptures, and the Mortification of the Toes and Feet”, L. Hawes, W. Clarke, and R. Collins,London.
5.Cook, J.W., Hewett, C.L. and Hieger, I., 1933. The isolation of cancer-producing hydrocarbon from coal tar, part I, II and III. Journal of Chemical Society, 395-421.
6.Dias, J.R., 1987. Handbook of Polycyclic Aromatic Hydrocarbons: Part A: Benzenoid Hydrocarbons. Elsevier press, Amsterdam.
7.Nishioka, M.G.., Lewtas, J., 1992. Quantification of nitro-and hydroxylatednitro-aromatic/polycyclic aromatic hydrocarbons in selected ambientair daytime winter sample. Atmospheric Environment 26,2077-2087.
8.Hecht, S.S., 1988. Potential carcinogenic effects of polynuclear aromatic hydrocarbon and nitroaromatic in moblic health, 555.
9.Behymer, T.D., Hites, R.A., 1985. Photolysis of polycyclic aromatic hydrocarbons adsorbed on simulated atmospheric particulates. Environmental Science & Technolgoy 19, 1004-1006.
10.Oliver, B.G.., Nilmi, A.J., 1998. Trophodynamic analysis of polychlorinated biphenyls congeners and other chlorinated hydrocarbons in the Lake Ontario. Environmental Science & Technology 4, 388-397.
11.Barron, M.C., 1990. Bioconcentration. Environmental Science & Technology 24, 1612-1618.
12.張碧芬、袁紹英，多環芳香聽化合物之環境流佈及其生物分解，環境檢驗通訊雜誌，專題報導第22期。
13.歐詠喆，2003，水浴加熱與微波輔助加熱頂空固相微萃取水樣品多環芳香烴碳氫化合物之研究，國立高雄師範大學碩士論文。
14.阮若屈、廖振傑，2001，「柴油的微生物分解」，化工技術，第9卷第2期，第229頁及第231-234頁。
15.游宗霖，2003，以純化菌種Candida viswanathii 處理海水中柴油多環芳香烴之研究，國立中山碩士論文。
16.陳富平，2004，大氣次微米微粒（PM1）多環芳香烴化合物（PAHs）之特性研究，國立高雄第一科技大學碩士論文。
17.行政院環保署，1996，廢棄物檢測方法：索氏萃取法，R113.00C。
18.行政院環保署，1996，廢棄物檢測方法：超音波萃取法，R114.00C。
19.U.S. EPA, 1996. Method 3545. Test Methods for Evaluating Solid Waste,　SW-846 update Ⅲ.
20.U.S. EPA, 1996 . Method 3560 ＆ 3561. Test Methods for Evaluating Solid Waste, SW-846 update Ⅲ.
21.U.S. EPA, 1996. Method 3546. Test Methods for Evaluating Solid Waste,　SW-846 update Ⅲ.
22.atherine, L., Pawliszyn, J., 1990. Solid Phase Microextraction with Thermal Desorption Using Fused Silica Optical Fibers. Anal. Chem. 62, 2145-2148.
23.Abu-Samia, A., Morris, J.S., Koirtyohann, S.R., 1975. Analytical Chemistry 47, 1475-1477.
24.Ganzler, K., Salgo, A., Valko, K., 1986. Microwave extraction a novel sample preparation method for chromatography. Journal of Chromatography 371, 299-306.
25.金欽漢、戴樹珊、黃卡瑪，2001，微波化學，科學出版社。
26.Kingston, H.M., Jassie, L.B., 1988. Introduction to microwave sample prearation. Washington DC., 7-31.
27.徐永源，「微波萃取綠色科技 Microwave-Assisted Processes 」，http://www.scienceh.org/Chinese/COrigin/Mag/June-2001/june-2001.htm。
28.許道平，1998，分析樣品前處理技術-微波萃取法，CHEMISTRY ( THE CHINESE CHEM. SOC. TAIPEI ) .，Vol. 56，No. 4，285-294。
29.Hileman, B., 1992. Ban on persistent toxic compounds urged. Chemical and Engineering News 6, 6.
30.洪志青，2000，開放式微波萃取土壤中多氯聯苯之研究，國立高雄師範大學碩士論文。
31.http://www.e-kohan.com.tw/。
32.鄭智元，2001，大氣降水中多環芳香烴的定量分析，國立中央大學碩士論文。
33.Alpendurada, M.de F., 2000. Review Solid Phase Microextraction: a promising technique for sample preparation in environmental analysis. Journal of Chromatography A. 889, 3-14.
34.Catherine, L., Pawliszyn, J., 1990. Solid Phase Microextraction with Thermal Desorption Using Fused Silica Optical Fibers. Anal. Chem. 62, 2145-2148.
35.Zhang, Z., Pawliszyn, J., 1993. Headspace Solid-Phase Microextraction. Anal. Chem. 65, 1843-1852.
36.SUPELCO, 1998. SUPELCO Chromatography products, 3223.
37.Arthur, C.L., Killam, L.M., Buchholz, K.D., Berg, J.R., Pawliszyn, J., 1992. Automation and Optimization of Solid-Phase Microextraction. Anal. Chem. 64, 1960.
38.Lord, H., Pawliszyn, J., 2000. Evalution of Solid-Phase Microextraction Technology. Journal of Chromatography A. 885, 153-193.
39.Zhang, Z., Pawliszyn, J., 1995. Quantitative Extraction Using an Internally Cooled Solid-Phase Microextraction Device. Anal. Chem. 67, 34-43.
40.Zhang, Z., Yang M.J., 1994. Pawliszyn. Anal. Chem. 66, 844A.
41.黃敬德、謝有容，1998，固相微萃取技術之原理及應用，化學，第56卷第4 期，311-318。
42.Louch, D., Motlagh, S., 1992. Pawliszyn. Anal. Chem. 64, 1187.
43.Jeannot, M.A., Cantwell, F.F., 1997. Anal. Chem. 69, 235-239.
44.Shen, G.., Lee, H.K., 2002. Hollow fiber-protected liquid-phase microextraction of trazine herbicides. Anal. Chem. 74, 648-654.
45.Michael, A.J., Frederick, F.C., 1997. Mass Transfer Characteristics of Solvent Extraction into a Single Drop at the Tip of a Syringe Needle. Anal. Chem. 69, 235-239.
46.Jiang, X.M., Lee, H.K., 2004. Anal. Chem. 76, 5591-5596.
47.施怡安，2003，以微波輔助頂空液相微萃取結合氣相層析法分析水中氯酚類污染物之研究，國立中興大學碩士論文。
48.謝文杰，2005，微波輔助頂空液相微萃取方法分析水樣品中半揮發性物質之研究，國立高雄師範大學碩士論文。
49.Hou, L., Lee, H.K., 2002. A pplication of static and dynamic liquid-phase microextraction in the determination of polycyclic aromatic hydrocarbons. Journal of Chromatography A. 976, 377-385.
50.Liu, J.F., Jiang, G.B., Chi, Y.G., Cai, Y.G., Zhou, Q.X., Hu, J.T., 2003. Use of Ionic Liquids for Liquid-Phase Microextraction of Polycyclic Aromatic Hydrocarbons. Anal.Chem. 75, 5870-5876.
51.Jiang, X., Basheer, C., Zhang, J., Lee, H.K., 2005. Dynamic hollow fiber-supported headspace liquid-phase microextraction. Journal of Chromatography A. 1087, 289-294.
52.黃雅苹，2004，微波輔助頂空固相微萃取方法分析水樣品中半揮發性物質之研究，國立高雄師範大學碩士論文。
53.C. Basheer, R.B., Lee, H.K., 2003. Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography–mass spectrometry. Journal of Chromatography A. 1016, 11–20.