大體積固相微萃取技術應用於被動式空氣採樣及動力學探討

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姓名

詹季儒(Ji-Ru Jame) 查詢紙本館藏

畢業系所

化學學系

論文名稱

大體積固相微萃取技術應用於被動式空氣採樣及動力學探討
(Large Volume Solid Phase Microextraction for passive air sampling)

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摘要(中)

本實驗利用增加靜相體積之概念，以提高分析物的萃取量，自行塗怖PDMS及PDMS/Carboxen高分子薄膜，其成分接近商業化固相微萃取(Solid phase microextraction)的吸附靜相，配合自行研發之進樣裝置，使熱脫附分析物不再侷限氣相層析儀(GC)之注射埠，大幅降低偵測極限。實驗過程中設計組裝一套熱脫附進樣系統，使用benzene、toluene、ethylbenzene、m-xylene、o-xylene (BTEX)純物質全量進樣作為校正曲線(calibration curves)，驗證此系統可達良好線性範圍(R2＞0.99)及再現性(1.07％)。
此外搭配自行設計頂空採樣裝置(headspace sampling device)分析濃度10 µg/L (ppb) BTEX樣品6次，其再現性4~12%。以及連續熱脫附方式，分析之同濃度BTEX，結果顯示分析物在PDMS及PDMS/Carboxen高分子薄膜脫附模式皆呈現指數下降曲線[Q/q0=exp(-aN)]符合典型之擴散行為，其PDMS及PDMS/Carboxen高分子薄膜感度對熱脫附次數存在良好的相關性(R2＞0.99)，並探討動力學常數a值對吸附及脫附效率之影響；且利用動力學常數，求得分析物在基質中的濃度及與靜相的分配常數，以及檢量未知空氣中BTEX的濃度。
近年來由於固相微萃取的材料特性與本身的構造設計，可以濃縮萃取揮發性物質，顯示了作為空氣採樣器的可能性，本實驗使用自製的PDMS及PDMS/Carboxen高分子薄膜作為被動式採樣器；以及頂空採樣裝置作為簡化空氣中變數，自製大體積PDMS及PDMS/Carboxen裝置無論對於標準樣品或真實空氣皆可達到良好的感度及解析度，尤其以PDMS/Carboxen對真實空氣效果更佳。

摘要(英)

This research is based upon a simple SPME (solid phase micro-extraction) theory, in which the sensitivity of SPME is proportional to the volume of the polymer phase, assuming the volume of the polymer phase is negligible compared to that of an aqueous sample. A thick film of polydimethylsiloxane (PDMS) polymer was coated on a glass rod of 2 mm O.D. x 6.7 cm length to serve as a large volume solid phase extraction medium for increasing sensitivity.
A renovated thermal desorption device was retrofitted from a regular GC injector to accommodate the thick PDMS rod. To cope with peak broadening in chromatography, an in-line micro-sorbent trap packed was installed prior to the capillary column to focus volatile analytes slowly desorbed from the large volume PDMS rod, resulting in highly resolved peaks.
By placing various amounts of high purity benzene, toluene, ethylbenzene, m-xylene, o-xylene (BTEX) into the thermal desorption device the linearity and precision of the injection system were effectively validated with R2 > 0.99 and RSD < 1.07%, which lays a solid ground for the subsequent quantitative and kinetic studies.
Throughout the experiment a headspace device was designed to generate standard gas mixture by equilibrating headspace with a standard aqueous solution containing target compounds of BTEX. The large volume SPME was able to achieve repeatability of 4~12% for BTEX, sufficient for high quality quantitative analysis.
Thermal desorption of the PDMS or PDMS/Carboxen rod showed a rapid exponential decline with the residue which can be described by the first order kinetics [Q/q0=exp(-aN)] and conformed to the diffusion theory. Herein, the kinetic constant can be described as the efficiency of sorption and desorption and has been shown to be temperature dependent but independent of extraction time and sample concentration. The simplified kinetics allows rate constants to be easily determined by arbitrarily loading and successive desorption of the target compounds at arbitrary extraction time. Using rate constants and equilibrium constants the concentrations of volatile analytes in both air and water can be easily calculated avoiding conventional time-consuming calibration procedures.
Both water and air samples were tested by the large volume SPME to show the sensitivity due to volume merit and the overall applicability of this self-developed technique.

關鍵字(中)

★ 被動式採樣
★ 大體積固相微萃取
★ 脫附
★ 聚二甲基矽氧烷
★ 動力學常數

關鍵字(英)

★ kinetic constant
★ polydimethylsiloxane (PDMS)
★ large volume solid phase microextraction
★ diffusion

論文目次

中文摘要 I
英文摘要 III
目錄 V
圖目錄 VIII
表目錄 XI
第一章前言 1
1-1 空氣中污染物採樣方法 1
1-2 固相微萃取 8
1-3 固相微萃取應用於被動式空氣採樣 14
1-4 研究目的 20
第二章大體積固相微萃取理論 24
2-1 平衡狀態下萃取 24
2-2 非平衡狀態下萃取 26
2-2.1 吸附 26
2-2.2 脫附 35
2-2.3 脫附vs. 吸附 41
2-3 分析物在基質中濃度(C0) 43
2-3.1分配常數(Kfs)求法 43
2-3.2平衡狀態下求得基質中的濃度 48
2-3.3非平衡狀態下求得基質中的濃度 49
第三章實驗設計 51
3-1 高分子薄膜塗佈 51
3-2 進樣前濃縮裝置 53
3-2.1樣品熱脫附槽 53
3-2.2系統之進樣濃縮裝置 55
3-3 頂空採樣裝置 58
3-4 全量進樣 60
3-5 標準溶液製備 62
第四章結果與討論 63
第一節動力學探討 63
4-1 全量進樣驗證線性與再現性 63
4-2 吸附特性探討 68
4-3 全量進樣與吸附特性比較 76
4-4 脫附特性探討 78
4-5 動力學常數a值的探討 89
4-5.1 動力學常數a值的求法 89
4-5.2 影響動力學常數a值之因子 92
4-5.3 溫度影響動力學常數a值 96
第二節大體積固相微萃取應用於被動式空氣採樣 99
4-1利用標準品比對定性 99
4-2 真實空氣 100
4-3 推算分析物在基質中的濃度 106
第五章總結 109
參考文獻 110

參考文獻

Radian Corp. Control techniques for volatile organic emissions from stationary source. USEPA, EPA-450/2-78-022, 1978.
Susanne V. H. Air sampling instruments for evaluation of atmospheric contaminants. 8th, Ohio, 1989.
沈健智等，1996，主動式與被動式採樣分析VOCs化合物之研究，清華大學原子科學碩士論文。
工業技術研究院，工業技術安全發展中心，物質安全資料表。
Hawthone, S.; Miller, D.; Arthur, C.; Pawliszyn, J. J. Chromatogr. 1992, 603, 185-191.
Wasowicz, E.; Kaminski, E.; Jelen, H.; Wlazly, K. J. Agric. Food Chem. 1998, 46, 1469-1473.
Singer, K.; Wenz, B.; Seefeld, V.; Seeper, U. German Lab-Med. 1995, 18, 112-118
Page, B.D.; Lacroix, G. J. Chromatogr. 1993, 648, 199-211.
Choudhury, T.; Gerhardt, K.; Mawhinney, T. Environ. Sci. Technol. 1996, 30, 3259-3265.
Muller, L.; Gorecki, T.; Pawliszyn, J. Anal. Chem. 1999, 64, 610-616
Koziel, J.; Jia, M.; Khaled, A. Trends in Anal. Chem. 1999, 400, 153-162.
Bao, M.; Pantani, F.; Griffini, O. J. Chromatogr., A 1998, 809, 75-87.
Arthur, C.; Pratt, K.; Belardi, R.; Motagh, S.; Pawliszyn, J. J. High Res. Chromatogr. 1992, 15, 741-744.
Migdic, C.; Pawliszyn, J. J.Chromatogr., A 1996, 723, 111-112.
Yang, Y.; Miller, D.J.; Hawthorne, S.B. J. Chromatogr., A 1998, 800, 1866.
Maria, L.; Ken, L.; Merv, F. Anal. Chem., 1998, 70, 2510-2515.
Chen, J.; Pawliszyn, J. Anal. Chem. 1995, 67, 2530-2563.
Daimon, H.; Pawliszyn, J. Anal. Chem. 1996, 33, 421-424.
Langenfeld, J.; Hawthorne, S.; Miller, D. J. Chromatogr., A 1996, 740, 139-145.
Pawliszyn, J. Applications of Solid Phase Microextraction. Royal Society of Chemistry: Cornwall, U.K., 1999.
Pawliszyn, J. Solid Phase Microextraction: Theory and Practice. Wiley-VCH: New York, 1997.
Arthur, C. L.; Pawliszyn, J. Anal. Chem. 1990, 62, 2145-2148.
Buchholz, K.D.; Pawliszyn, J., Anal.Chem. 1994, 66, 160-167.
Prosen, H.; Zupancic-Kraij, L., Trends in Anal. Chem. 1999, 18, 272-282.
Gang, S.; Hian K. L. J. Anal. Chem. 2003, 75, 98-103.
Fustinoni, S.; Giampiccolo, R.; Pulvirenti, S.; Buratti, M.; Colombi, A. Journal of Chromatogr., B 1999, 723, 105-115.
Koziel, J. A.; Novak, I. Trends in Anal. Chem. 2002, 21, 840-850.
Meng, C.; Janusz, P. Environ. Sci. Technol. 1995, 29, 693-701.
Koziel, J.; Jia, M.; Pawliszyn, J. Anal. Chem. 2000, 72, 5178-5186
Martos, P. A.; Pawliszyn, J.; Anal. Chem. 1999, 71, 1513-1520.
Hook, G. L.; Kimm, G. L.; Hall, T.; Smith, P. A. Trends in Anal. Chem. 2002, 21, 534-543.
Koziel, J.A.; Noah, J.; Pawliszyn, J. Environ. Sci. Technol. 2001, 35, 1481-1486.
Martos, P. A.; Pawliszyn, J. Anal. Chem. 1998, 70, 2311-2320.
Grote, C.; Pawliszyn, J.; Anal. Chem. 1997, 69, 587-596.
Chen, Y.; Pawliszyn, J. Anal. Chem. 2003, 75, 2004-2010.
Xiong, G,; Koziel, J. A.; Pawliszyn, J. J. Chromatogr., A 2004, 1025, 57–62
Xia, X.; Leidy, R.B. Anal. Chem. 2001, 73, 2041-2047.
Khaled, A.; Pawliszyn, J. J. Chromatogr., A 2000, 892, 455-467.
Elke, K.; Jermann, E.; Begerow, J.; Dunemann, L. J. Chromatogr., A 1998, 826, 191-200.
Koziel, J.A.; Khaled, A.; Noah, J.; Pawliszyn, J. Anal. Chim. Acta 1999, 400, 153-162.
Koziel, J.A.; Pawliszyn, J. J. Air Waste Manag. Assoc., 2001, 51, 173-184.
Harper, M. J. Chromatogr., A 2000, 885, 129-151.
Benijts, T.; Vercammen, J.; Dams, R.; Tuan, H.P.; Lambert, W.; Sanddra, P. J. Chromatogr., B 2000, 755, 137-142.
Ai, J. Anal. Chem.1997, 69, 1230-1236.
Ai, J. Anal. Chem. 1997, 69, 3260-3266.
Ai, J. Anal. Chem. 1998, 70, 4822-4826.
Oomen, A. G.; Mayer, P.; Tolls, J.; Anal. Chem. 2000, 72, 2802-2808.
Bartelt, R. J.; Zilkowski, B. W. Anal. Chem. 1999, 71, 92-101.
陳元曼，2003，大體積固相微萃取水中揮發性有機污染物，
中央大學化學所碩士論文。
Chen, Y.; Pawliszyn, J. Anal. Chem. 2004, in press.
Zhang, Z.; Pawliszyn, J. J. Phys. Chem. 1996, 100, 17648-17654.
Kamil, K.; Miroslav, C.; Jirí, M. J. Chromatogr., A 2004, 1029, 263–266.
陳韋立，2000，大氣及水樣中揮發性有機氣體自動化分析技術之建立與應用, 中央大學碩士論文。
Elke, K.; Jermann, E.; Begerow, J.; Dunemann, L. Journal of Chromatogr., A 1998, 826, 191-200.
Gorecki, T.; Yu, X.; Pawliszyn, J. Analyst, 1999, 124, 643-649.
Alpendurada, M. J. Chromatogr., A 2000, 889, 3-14.
57 Chen, Y.; Koziel, J. A.; Pawliszyn, J. Anal. Chem. 2003, 75, 6485-6493.
58 Lestremau, F.; Andersson, F.A.; Desauziers, V.; Fanlo, J.L. Anal. Chem. 2003, 75, 2626-2632.
59 Koziel, J.A.; Odziemkowski, M.; Pawliszyn, J. Anal. Chem. 2001, 73, 47-54.
60 美國EPA網站
http://www.epa.gov/athens/learn2model/part-two/onsite/esthenry.htm

指導教授

王家麟(Jia-Lin Wang)

審核日期

2004-6-29

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