臺灣博碩士論文加值系統

氟氯碳化物(chlorofluorocarbon ; CFC)，因長生命期及化性穩定，一旦排放後會穩定漂至平流層破壞臭氧。隨著蒙特婁協議禁用氟氯碳化物，其取代品-氫氟氯碳化物(hydrochlorofluorocarbon ; HCFC)和氫氟碳化物(hydrofluorocarbon ; HFC)的使用量與日俱增 ，雖不致破壞臭氧，卻是極強的溫室效應氣體，面對全球暖化劇變。人們開始注意此三類物種排放。
本研究將對三類物種作量測方法開發和結合野外長期監測研究三類物種在台灣的排放情形，以化學吸附劑前濃縮系統搭配二維氣相層析技術作為監測氟氯碳化物的基本分析方法，但ECD對HCFC和HFC偵測感度不佳，我們使用綴氧法(Oxygen Doping)於ECD中，形成綴氧電子捕獲偵檢器(Doping ECD)，提高此兩類取代物的靈敏度，使用管柱為PoraPLOT-Q+ PLOT雙管柱。此法優點為易於定性和定量，且系統簡單低廉，適合至野外架設長期監測站。
將開發完成的方法應用於野外長期監測，在雲林台西監測針對CFC、HCFC和HFC作為期一個月的長期監測，在中大氣象站無排放的CF2ClCFCl2和CCl4在此區測得些許人為排放，其中CCl4明顯受東北風影響甚鉅；同樣受東北風影響物種CH2Cl2，濃度高達8 ppb；其餘物種如CF2Cl2、CF2CBr和CHCl3也測得人為排放。將監測數據以高斯分佈概念研析鹵碳化物的排放情形，發現物種若無人為排放，則數據符合高斯分佈；若存在人為排放，則呈現非高斯分佈，且整體分佈明顯傾向正偏差。

The continual anthropogenic chlorofluorocarbons (CFCs) are known to destroy stratospheric ozone because of their long lifetimes and chemical stability. The advent of the Montreal Protocol caused total phase-out of CFCs in 1996. The consumption of the replacements, hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), have been increasing rapidly. Although they have limitted or no ozone depleting potentials (ODPs), they are very potent green house gases.
In this study, a gas chromatographic (GC) method was developed to simultaneously measure CFCs, HCFCs and HFCs in the atmosphere. The system involved an automated preconcentration unit using chemical adsorbents combined with two dimensional GC equipped with electronic captured detector (ECD) for measuring CFCs. For HCFCs and HFCs the oxygen-doping ECD method was employed to enhance the sensitivity.
The system was tested on campus and at the Taishi EPA monitoring station. Limited emissions of CF2ClCFCl2 and CCl4 were found, which can serve as a useful quality assurance tool to validate measurements. Other more variable species, i.g., CF2Cl2, CF2ClBr and CHCl3, were detected revealing the existence of sources. For the doping system deployed in Taishi station, strong emissions of CH2Cl2 with concentration excess of 8 ppb relative to the baseline condition was found.
The datasets were further examined by Gaussian distribution, which is a novel approach to reveal variability and sources of halocarbons.

目 錄
中文摘要
英文摘要
謝誌
目錄
圖目錄
表目錄
第一章 前言
1-1 研究緣起……………………………………………………...1
1-2 CFC介紹…………..………………………………………….2
1-3 HCFC介紹………….……..………………………………….6
1-4 臭氧破壞潛勢(ODP)和全球暖化潛能(GWP)…..…………..9
1-5 我國現狀…………………………………………………….12
1-6 研究動機…………..………………………………………...14
第二章 文獻回顧……………………………………………………..15
2-1 研究背景………………………………..…………………...15
2-2 背景量測介紹…………………..…………………………...16
2-2-1 國際背景監測-英國Bristol……….…………...…….16
2-2-2 國際背景監測-NOAA/ESRL………………..………20
2-2-3 國際背景監測-UCI…………………………..……...24
2-3 非背景量測介紹…………………………..………………...25
2-3-1 非背景量測研究………………………………..……..25
2-3-2 非背景量測-本實驗室現有技術………..……………28
2-4 綴氧法 (Oxygen Doping)………………………..……..…...29
第三章 實驗方法與分析結果………………………………………..33
3-1 CFC迴圈濃縮法………….…..…………………………...33
3-1-1 實驗原理…...……..…………………………………...34
3-1-2 吸附管製作……….…………….……………………..35
3-1-3 迴圈濃縮系統……………..………………..…………37
3-1-4 層析方法介紹……………………..…………………..42
3-2 CFC 直接濃縮法…………………………..………………...46
3-2-1 直接濃縮系統………………..…………...…………...46
3-2-2 直接濃縮法體積檢量……..……..…………………....51
3-3 HCFC 直接濃縮綴氧法…………...………………………...55
3-3-1 實驗原理……………………..………………………..55
3-3-2 分析方法……………………………..………………..56
3-3-3 綴氧最佳化實驗………………………………………61
3-3-4 綴氧法之體積檢量……………………………………65
3-4 結論…………..……………………………………………...67
第四章 野外實測………………………………………..……………68
4-1 CFC 野外長期監測…………………………..………...……68
4-1-1 中大氣象測站…………………………...…………….68
4-1-2 結果與討論……………………………………………69
4-1-3 小結……………………………………………………..91
4-2 HCFC 野外長期監測………………...…………..……….....92
4-2-1 雲林台西測站…………..………………………............92
4-2-2 結果與討論…………………………...………………...93
4-2-3 小結………....................................................................108
第五章 數據討論................................................................................109
5-1 量測數據比較…………………………….………………..109
5-2 高斯分佈解釋人為排放…………………………….….….112
5-2-1 中大氣象站量測數據…………………….…………114
5-2-2 雲林台西量測數據…………………………………..118
5-3 小結…….…………………………………………………..123
第六章 總結……………….…………….…………………………..124
第七章 參考文獻……………………………………………………125

[1]Molina, M. J.; Rowland, F. S. Stratospheric sink for chlorofluoro- methanes : chlorine atomic-atalysed destruction of ozone Nature, 1974, 249, 810-812.

[2]Jager, D. D. Safeguarding Ozone Layer and the Global Climate system：Issues Related to Hydrofluorocarbons and Perfluorocarbons IPCC Summer Report Technical summary, 2007.

[3]http://toms.gsfc.nasa.gov/ozone/ozone_v8.html Total Mapping Spectrometer.

[4] Parson, E. A. Protecting the ozone layer : science and strategy, Oxford; New York : Oxford University Press, 2007.

[5] www.qf.nthu.edu.tw/~jtyang/frmc/KP_ppt.pdf

[6] 財團法人國改研究基金會國改研究報告,2001.11.15.

[7]各國HCFCs管制資訊與全球替代狀況 工業技術研究院2006. 10.16.

[8] AGAGE website http://agage.eas.gatech.edu/

[9] Prinn, R. G.; Weiss, R. F.; Miller, B. R.; Huang, J.; Alyea, F. N.; Cunnold, D. M.; Fraser, P. J.; D. E. Hartley, D. E.; Simmonds P. G. Atmospheric trends and lifetime of CH3CCI3 and global OH concentrations Science. 1995, 269, 187-192.

[10] http://www.esrl.noaa.gov/gmd/hats/

[11] http://www.physsci.uci.edu/~rowlandblake/research_atmos.html

[12] Barletta, B.; Meinardi, S.; Simpson, I. J.; Rowland, F. S.; Chan, C. Y.; Wang, X.; Zou, S.; Chan, L. Y.; Donald.; Blake. D. R. Ambient halocarbon mixing ratios in 45 chinese cities Atmos. Environ., 2006, 40, 7706-7719.

[13] Chang, C. C.; Lai, C. H.; Wang, C. H.; Liu, Y.; Zhang Y.; Wang, J. L. Variability of anthropogenic ozone depleting substances as an indicator of emission status in china Atmos. Environ (accepted)

[14]張志忠, 鹵碳化物分析系統之建立與實際大氣量測, 碩士論文, 中央大學化學研究所, 1997.

[15] Wang, J. L.; Chang, C. J.; Chang, W. D.; Chew,; C. Shin-wei Chen, S. W. Construction and evaluation of automated gas chromatography for the measurement of anthropogenic halocarbons in the atmosphere J. Chromatogr. A. 1999, 844, 259-269

[16]華希哲, 利用GC/MS分析大氣中CFCs取代物(HCFC與HFC)及揮發性有機化合物, 碩士論文, 中央大學化學研究所, 1998.

[17]Wang, J. L.; Lin, W. C.; Chen, T. Y. Using atmospheric CCl4 as an internal reference in gas standard preparation Atmos. Enviro., 2000, 34, 4393-4398.

[18]吳政修, 鹵碳化物自動化分析系統之建立與應用, 碩士論文, 中央大學化學研究所, 2001.

[19] Grimsrud, E. P.; Miller, D. A. Oxygen doping of carrier gas in measurement of halogenated methanes by Gas Chromatography with electron capture detection. Anal. Chem. 1978, 50, 1141-1145.

[20]Grimsrud, E. P.; Miller, D. A. Correlation of electron capture response by oxygen with chemical structure for chlorinated Hydrocarbons. Anal. Chem. 1979, 51, 851-858.



[21] Sanchez, J.M., Sacks, R.D. On-line multibed sorption trap and injector for the GC analysis of organic vapors in large-volume, air samples Anal. Chem. 2003, 75, 978-985.

[22] Supelco商業化型錄, 2007-2008.

[23]Karbiwwnyk, C.M.; Miles, C. M.; Helmig, D.; Birks, J. W. Use of chloroflurocarbons as internal standards for the measurement of atmospheric non-methane volatile organic compounds sampled onto solid adsorbent cartridges. Environ. Sci. Technol. 2003, 37, 1002-1007.

[24] Krol, M. C.; Lelieveld, J.; Oram, D. E.; Sturrock, G. A.; Penkett, S.A.; Brenninkweijer, C. A. M.; Gros, Williams, V. J. Scheeren, H. A. Continuing emissions of methyl chloroform from Europe. Nature, 2003, 421, 131-135.

[25] Google map satellite. http://www.google.com/help/maps/tour/

[26]Miller, B. R.; Weiss, R. F.; Salameh, P. K.; Tanhua, T.; Greally, B. R.; Mühle, J.; Simmonds, P. Medusa : A sample preconcentration and GC/MS detector system for in-situ measurements of atmospheric trace halocarbons, hydrocarbons, and sulfur compounds. Anal. Chem. 2008, 80, 1536-1545.

[27]Barletta B., Meinardi S., Simpson I.J.; Khwaja, H. A.; Blake. D. R.; Rowland F. S. Mixing ratios of volatile organic compounds in the atmosphere of Karachi, Pakistan. Atmos. Environ., 2002, 36, 3429–3443.