臺灣博碩士論文加值系統

本研究目標為建立一套以液相層析質譜儀精確地定性與定量動物檢體和環境水樣中perfluoropentanoic acid（PFPeA）、perfluorooctanoic acid（PFOA）、perfluorodecanoic acid（PFDA）、perfluorobutanesulfonate（PFBS）和perfluorooctanesulfonate（PFOS）等五種全氟界面活性劑之分析方法。液相層析儀動相是以甲醇和醋酸銨溶液組成。環境水樣前處理部份是以C18萃取管柱進行固相萃取法達到淨化濃縮目的；生物檢體前處理是以甲基第三丁基醚（MTBE）進行液-固相萃取法達到濃縮目的。實驗結果顯示PFPeA、PFBS、PFOA、PFOS和PFDA在水樣中的定量極限（LOQ）分別為6 ng/L、2 ng/L、2 ng/L、0.5 ng/L和2 ng/L。在14個不同環境水樣採樣點中，有11個採樣點被檢測到含有全氟界面活性劑，檢測率可高達79%，且PFOA、PFOS和PFDA被檢測最高總濃度可達到450 ng/L。動物檢體中PFPeA、PFBS、PFOA、PFOS和PFDA的定量極限分別為50 ng/g、20 ng/g、20 ng/g、5 ng/g和20 ng/g。動物檢體均可偵測到全氟界面活性劑，且PFOA、PFOS和PFDA被檢測最高總濃度可達到 1100 ng/g。

A method for the determination of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA) in various water and biological tissue samples was developed and validated in this study. The contents of PFCs in water samples were extracted by C18 solid-phase extraction (SPE). The biological tissue samples (frozen-dried fish and oysters) were simply extracted by liquid-solid extraction with MTBE and adding tetrabutylammonium hydrogensulfate (TBA) as an ion-pairing reagent. The analytes were then identified and quantitated by liquid chromatography-ion trap negative electrospray mass spectrometry (LC-ESI ion-trap-MS). Limits of quantitation (LOQ) were established between 0.5 to 6 ng/l in 250 ml of water sample, while 5 to 50 ng/g (dry weight) for biological tissue sample. Intrabatch and interbatch precision with their accuracy at two concentration levels were also investigated. Precision for these three PFCs, as indicated by RSD, proved to be less than 11 and 17%, respectively. The total contents of PFOA, PFOS and PFDA were detected in concentrations of up to 450 ng/l in various water samples, while up to 1100 ng/g in fish and oyster samples. PFOA and PFDA was the major PFCs detected in water samples and biological tissue samples, respectively.

中文摘要 ------------------------------------------------------------------ Ⅰ
英文摘要 ------------------------------------------------------------------ Ⅱ
目錄 ----------------------------------------------------------------------- Ⅲ
表目錄 -------------------------------------------------------------------- Ⅵ
圖目錄 -------------------------------------------------------------------- Ⅶ
第一章 前言 ----------------------------------------------------------- 1
1-1 研究源起 ------------------------------------------------------- 1
1-2 研究目標 ------------------------------------------------------- 6
第二章 文獻回顧 ----------------------------------------------------- 8
2-1 全氟界面活性劑 ---------------------------------------------- 8
2-1-1 全氟界面活性劑簡介 --------------------------------- 8
2-1-2 全氟界面活性劑之性質 ------------------------------ 9
2-1-3 全氟界面活性劑之毒性 ------------------------------ 11
2-1-4 國外對全氟界面活性劑之相關研究 -------------- 14
2-2 液相層析質譜儀 ---------------------------------------------- 22
2-2-1 質譜儀之游離技術發展 ----------------------------- 22
2-2-2 電噴灑游離法之歷史發展 -------------------------- 24
2-2-3 電噴灑游離法原理及反應機構 -------------------- 26
2-2-4 電噴灑游離法之影響液滴形成因素 -------------- 31
2-2-5 電噴灑游離法之基質效應及訊號與濃度關係 -- 32
2-2-6 電噴灑游離法之優點 -------------------------------- 33
2-2-7 離子阱質量分析器原理 ----------------------------- 34
第三章 實驗步驟與樣品分析 -------------------------------------- 37
3-1 實驗藥品與儀器設備 ---------------------------------------- 37
3-1-1 實驗藥品 ----------------------------------------------- 37
3-1-2 儀器設備 ----------------------------------------------- 39
3-2 實驗步驟 ------------------------------------------------------- 40
3-2-1 標準品的製備 ----------------------------------------- 40
3-2-2 全氟界面活性劑的檢測 ----------------------------- 40
3-2-3 水樣之萃取步驟 -------------------------------------- 43
3-2-4 動物樣品之萃取與淨化 ----------------------------- 45
第四章 結果與討論 -------------------------------------------------- 46
4-1 液相層析質譜儀對全氟界面活性劑之分析 ------------- 46
4-1-1 動相組成溶劑對於分析物感度之影響 ------------- 46
4-1-2 霧化器壓力對於分析物感度之影響 ---------------- 47
4-1-3 乾燥氣體流速及乾燥氣體溫度對於分析物感度之影響
--------------------------------------------------------------- 48
4-1-4 毛細管電壓對於分析物感度之影響 -------------- 50
4-1-5 全氟界面活性劑之測定 ----------------------------- 51
4-1-6 檢量線製作 -------------------------------------------- 56
4-1-7 二次質譜定性分析 ----------------------------------- 58
4-2 測定不同環境中全氟界面活性劑的濃度 ---------------- 61
4-2-1 固相萃取管柱選擇 ----------------------------------- 61
4-2-2 不同水樣基質的全氟界面活性劑回收率探討 ---- 63
4-2-3 環境中全氟界面活性劑分析 ----------------------- 70
4-3 測定不同生物檢體中全氟界面活性劑的濃度 ---------- 81
4-3-1 不同生物檢體的全氟界面活性劑回收率探討 -- 81
4-3-2 生物檢體中全氟界面活性劑分析 ----------------- 85
第五章 結論與建議 -------------------------------------------------- 92
5-1 結論 ------------------------------------------------------------- 92
5-2 建議 ------------------------------------------------------------- 93
參考文獻 ----------------------------------------------------------------- 94
表目錄
表1-1 內標準品及標準品之結構式與縮寫 ---------------------- 5
表2-1 國外針對全氟界面活性劑化合物之水樣相關研究 ----- 16
表2-2 國外針對全氟界面活性劑化合物之動物樣品相關研究 18
表4-1 標準品與內標之主要選擇離子 ----------------------------- 57
表4-2 五種分析物之檢量線線性關係與相對標準偏差值 ----- 57
表4-3 五種分析物之偵測極限與定量極限 ----------------------- 57
表4-4 三種固相萃取劑對全氟界面活性劑回收率之比較 ----- 62
表4-5 分析物在不同水樣中之回收率與相對標準偏差值 ----- 65
表4-6 Intrabatch & Interbatch 精確度測試 ------------------------ 65
表4-7 全氟界面活性劑在不同水樣中的濃度 -------------------- 72
表4-8 全氟界面活性劑在不同國家之地表水濃度比較 -------- 73
表4-9 全氟界面活性劑在不同海域濃度比較 -------------------- 74
表4-10 分析物在不同生物檢體中之回收率與相對標準偏差值 82
表4-11 全氟界面活性劑在不同生物檢體中的濃度 ---------- 86
表4-12 全氟界面活性劑在不同地區魚類濃度比較 ---------- 87
表4-13 全氟界面活性劑在不同國家的牡蠣濃度比較 ------- 87
圖目錄
圖2-1 電噴灑游離法 -------------------------------------------------- 27
圖2-2 泰勒錐 ----------------------------------------------------------- 27
圖2-3 液滴形成離子過程 -------------------------------------------- 28
圖2-4 (a)電荷殘留模式；(b)離子揮發模型；(c)1993 年芬恩修正的離
子揮發理論 ----------------------------------------------------- 30
圖2-5 .離子阱構造 ----------------------------------------------------- 35
圖4-1 不同濃度之醋酸銨溶液對分析物感度之影響 ----------- 46
圖4-2 霧化器壓力對分析物感度之影響 -------------------------- 47
圖4-3 乾燥氣體流速對分析物感度之影響 ----------------------- 49
圖4-4 乾燥氣體溫度對分析物感度之影響 ----------------------- 49
圖4-5 毛細管電壓對分析物感度之影響 -------------------------- 50
圖4-6 分析物標準品以ESI 負離子模式分析之質譜圖 -------- 52
圖4-7 全氟界面活性劑與內標準品之選擇離子層析圖 -------- 55
圖4-8 經由核磁共振光譜確認後的PFOS結構異構物之結構式 55
圖4-9 分析物標準品以ESI 負離子模式分析之二次質譜圖 --- 59
圖4-10 添加全氟界面活性劑於不同水樣之層析圖 ------------- 66
圖4-11 水樣之選擇離子層析圖 ------------------------------------- 75
圖4-12 水樣之ESI 負離子模式分析二次質譜圖比較 ----------- 79
VII
圖4-13 添加全氟界面活性劑於生物檢體之層析圖 ------------- 83
圖4-14 生物檢體之選擇離子層析圖 ------------------------------- 88
圖4-15 生物檢體之ESI 負離子模式分析二次質譜圖比較 ----- 90

李茂榮、張榮森：電灑游離法原理及應用簡介，科儀新知，第14
卷5 期，第70-77 頁，民國82 年。
􀁺 林孝道：化學游離法質譜術科儀新知，第12 卷2 期，第38-47
頁，民國79 年。
􀁺 AlekSendrov, M. L.; Gall, L. N.; Shkurov, V. A.; Pavlenko, V. A.;
Krasnov, N. V.; Nikolaev, V. I., Mechanism of Ion Formation during
the Electrohydrodynamic Sputtering of a Liquid into a Vacumm, J.
Anal. USSR., 1984, 39, 1268.
􀁺 Austin, M. E.; Kasturi, B. S.; Barber, M.; Kannan, K.; Mohankumar,
P. S.; Mohankumar, S. M. J., Neuroendocrine effects of perfluorooctane
sulfonate in rats, Environmental Health Perspectives, 2003,
111, 1485-1489.
􀁺 Avery, M.J., Quantitative characterization of differential ion
suppressionn on liquid chromatography/atmospheric pressure
ionization mass spectrometric bioanalytical methods, Rapid Commun.
Mass Spectrom., 2003, 17, 197-201.
􀁺 Boulanger, B.; Vargo, J.; Schnoor, J. L.; Hornbuckle, K. C., Detection
of perfluoroctane surfactants in Great Lakes water, Environ. Sci. &
Technol., 2004, 38, 4064-4070.
􀁺 Bruin, A. P.; Covey, T. R.; Henion, J. D., Ion-spray interface for
combind liquid chromatography / atomospheric pressure ionization
mass spectrometry, Anal. Chem. 1987, 59, 2642-2646.
􀁺 Bruins, A.P., Mechanistic aspects of electrospray ionization, J.
Chromatogr. A, 1998, 794, 345-357.
􀁺 Cole, R. B., Electrospray ionization mass spectrometry, John Wiley
& Sons, Ltd., 1997
􀁺 Dole, D.; Mack, L. L.; Hines, R. L.; Mobley, R. C.; Ferguson, L. D.;
Alice, M. B., Evidence of charge inversion in the reaction of single
charged anion with multiply charged macroions, J. Chem. Phys.,
1968, 49, 2240-2249.
􀁺 Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F. ; Whitehouse, G. M.,
Electrospray Ionization for mass spectrometry of large biomolecules,
Science 1989, 246, 64-71.
􀁺 Fenn, J. B., Ion formation from charged droplets : role of geometry
energy and time, J. Am. Soc. Mass Spectrom., 1993, 4, 524-535.
􀁺 Gangl, E.T.; Annan, M.; Spooner, N.; Vouros, P., Reduction of signal
suppression effects in ESI-MS using a nanosplitting device, Anal.
Chem., 2001, 73, 5635-5644.
􀁺 Giesy, J. P.; Kannan, K., Global distribution of perfluorooctane
sulfonate in wildlife, Environ. Sci. & Technol., 2001, 35, 1339-1342.
􀁺 Giesy, J. P.; Kannan, K., Perfluorochemical surfactants in the
environment, Environ. Sci. & Technol., 2002, 147A-152A.
􀁺 Gomez, A.; Tang, K., On the structure of an electrostatic spray of
monodispers droplet, Phys. Fluid., 1994, 6, 404-414.
􀁺 Hagen, D. F.; Belisle, J,; Johnson, J. D.; Venkateswarlu, V.,
Characterization of fluorinated metabolites by a gas chromatographic-
helium microwave plasma deteror--the biotransformation of
1H, 1H, 2H, 2H-perfluorodecanol to perfluorooctanoate, Anal.
Biochem., 1981, 118, 336-343.
􀁺 Hansen K. J.; Cleman, L. A.; Ellefson, M. E.; Jonhson, H. O.,
Compound-Specific, quantitative characterization of organic fluorochemicals
in biological matrices, Environ. Sci. & Technol., 2001, 35,
766-770.
􀁺 Hansen, K. J.; Johnson, H. O.; Eldridge, J. S.; Butenhoff, J. L.; Dick,
L. A., Quantitative characterization of trace level of PFOS and PFOA
in the Tennessee River, Environ. Sci. Technol., 2002, 36, 1681-1685.
􀁺 Hu, W.; King, L.E.; Jones, P.D.; Giesy, J. P., Measurement of effects
of perfluorinated compounds on cell membrane fluidity by flow
cytometry, Abstracts of the SETAC Annual Meeting, Nashville, TN,
Nov. 2000; SETAC: Pensacola, FL.
􀁺 Hu, W.; Jones, P.D.; Upham, B. L.; Trosko, J.E.; Lau, C.; Giesy, J. P.,
Inhibition of gap junctional intercellular communication by
perfluorinated compounds in rat liver and dolphin kidney epithelial
cell lines in vitro and Sprague-Dawley rats in vivo, Toxicological
Sciences, 2002, 68, 429-436.
􀁺 Ikonomou, M. G.; Blades, A. T.; Kebarle, P., Electrospray – ion spray :
a comparison of mechanisms and performance, Anal. Chem., 1991,
63, 1989-1998.
􀁺 Iribarne, J. V.; Thornson, B. A., On the evaporation of small ion from
charged droplets, J. Chem. Phys., 1976, 64, 2284-2287.
􀁺 Kannan, K.; Farnson, J. C.; Bowerman, W. W.; Hansen, K. J.; Jones,
P. D.; Giesy, J. P., Perfluorooctane sulfonate in fish-eating water birds
including bald eagles and albatrosses, Environ. Sci. & Technol., 2001,
35, 3065-3070.
􀁺 Kannan, K.; Koistinen J.; Beckmen, K.; Evans, T.; Gorzelany, J. F.;
Hansen, K. J.; Jones, P. D.; Helle, E.; Nyman, M.; Giesy, J. P.,
Accumulation of perfluorooctane sulfonate in marine mammals,
Environ. Sci. & Technol., 2001, 35, 1593-1598.
􀁺 Kannan, K.; Choi, J. W.; Iseki, N.; Senthilkumar, K.; Kim, D. H.;
Masunaga, S.; Giesy, J. P., Concentrations of perfluorinated acids in
livers of birds from Japan and Korea, Chemosphere, 2002, 49,
225-231.
􀁺 Kannan, K.; Hansen, K. J.; Wade, T. L.; Giesy, J. P., Perfluorooctane
sulfonate in oysters, crassostrea virginica, from the Golf of Mexico
and the Chesapeake Bay, USA, Arch. Environ. Contam. Toxxicol.,
2002, 42, 313-318.
􀁺 Kannan, K.; Newsted, J.; Halbrook, R. S.; Giesy, J. P., Perfluorooctanesulfonate
and related fluorinated hydrocarbons in mink and
river otters from the United States, Environ. Sci. & Technol., 2002, 36,
2566-2571.
􀁺 Kannan, K.; Corsolini, S.; Falandysz, J.; Oehme, G.; Focardi, S.;
Giesy, J. P., Perfluorooctanesulfonate and related fluorinated
hydrocarbons in marine mammals, fishes, and birds from coasts of
the Baltic and the Mediterranean Seas, Environ. Sci. & Technol.,
2002, 36, 3210-3216.
􀁺 Kuehl, D. W.; Rozynov, B., Chromatographic and mass spectral
studies of perfluorooctanesulfonate and three perfluorooctane
sulfonamides, Rapid Commun. Mass Spectrom., 2003, 17,
2364-2369.
􀁺 Martin, J. W.; Kannan, K.; Berger, U.; Voogt, P.V.; Field, J.; Franklin,
J.; Giesy, J. P.; Harner, T.; Muir, D. C. G.; Scott, B.; Kaiser, M.;
JÄrnberg, U.; Jones, K. C.; Mabury, S. A.; Schroeder, H.; Simcik, M.;
Sottani, C.; Bavel, B. V.; KÄrrman, A.; Lindström, G.; Leeuwen, S.
V., Analytical challenges hamper perfluoroalkyl research, Environ.
Sci. & Technol., 2004, 249A-255A.
􀁺 Mallet, C.R.; Lu, Z.; Mazzeo, J.R., A study of ion suppression effects
in electrospray ionization from mobile phase additives and solidphase
extracts, Rapid Commun. Mass Spectrom., 2004, 18, 49-58.
􀁺 Moody, C. A.; Field, J. A., Determination of perfluorocarboxylates in
groundwater impacted by fire-fighting activity, Environ. Sci. &
Technol., 1999, 33, 2800-2806.
􀁺 Moody, C. A.; Field, J. A., Perfluorinated surfactants and the
environmental implications of their use in fire-fighting foams,
Environ. Sci. & Technol., 2000, 34, 3864-3870.
􀁺 Moody, C. A.; Kwan, W. C.; Martin, J. W.; Muir, D. C. G.; Mabury, S.
A., Determination of perfluorinated surfactants in surface water
samples by two independent analytical techniques: liquid
chromatography tandem mass spectrometry and 19F NMR, Anal.
Chem., 2001, 73, 2200-2206.
􀁺 Moody, C. A.; Martin, J. W.; Kwan, W. C.; Muir, D. C. G.; Mabury,
S. A., Monitoring perfluorinated surfactants in biota and surface
water samples following an accidental release of fire-fighting foam
into Etobicoke Creek, Environ. Sci.& Technol., 2002, 36, 545-551.
􀁺 Nier, A. O., Electron Impact Mass Spectrometry, Rev. Sci. Instrum.
1947, 18, 398-411.
􀁺 Ohya, T.; Kudo, N.; Suzuki, E.; Kawashima, Y., Determination of
perfluorinated carboxylic acids in biological samples by high-
performance liquid chromatography, J. Chromatogr., 1998, 720, 1-7.
􀁺 Olivares, J. A.; Nguyen, N. T.; Yonker, C. R.; Smith, R. D., On-line
Mass Spectrometric Detection for Capillary Zone Electrophoresis,
Anal. Chem. 1987, 59, 1230-1232.
􀁺 Olsen, G. W.; Burris, J. M.; Mandel, J. H.; Zobel, L. R., Serum
perfluorooctane sulfonate and hepatic and lipid clinical chemistry
tests in fluorochemical production employees, J. Occup. Environ.
Med., 1999, 41, 799-806.
􀁺 Olsen, G. W.; Hansen, J. K.; Stevenson, L. A.; Burris, J. M.; Mandel,
J. H., Human donor liver and serum concentrations of perfluorooctanesulfonate
and other perfluorochemicals, Environ. Sci. &
Technol., 2003, 37, 888-891.
􀁺 Renner, R., Perfluorinated compounds linked to carcinogenicity in
vitro, Environ. Sci. & Technol., 2001,35, 180A.
􀁺 Renner, R., Evidence that perfluorinated surfactant biocuumulate,
Environ. Sci. & Technol., 2002,36, 54A-55A.
􀁺 Renner, R., Concerns over common perfluorinated surfactant,
Environ. Sci. & Technol., 2003, 201A-202A.
􀁺 Rollgen, F.W.; Bramer-Wegner, E.; Butfering, L., Field-ion emission
from liquid solution-ion evaporation against electrohydrodynamic
disintegration, J. Phys., 1987, 48, 253-256.
􀁺 Saito, N.; Harada, K.; Inoue, K.; Sasaki, K; Yoshinaga, T.; Koizumi,
K., Perfluorooctanoate and perfluorooctane sulfonate concentrations
in surface water in Japan, J. Occup Health, 2004, 46, 49-59.
􀁺 Schröder, H. F., Fluorine-containing surfactants–a further challenge
for the environment, Vom Wasser, 1991, 77, 277.
􀁺 Smith, R. D.; Loo, J. A.; Edmonds, C. G.; Barinaga, C. J.; Udseth, H.
R., New developments in biochemical mass spectrometry: electrospray
ionization, Anal. Chem., 1990, 62, 882-889.
􀁺 So, M. K.; Taniyasu, S.; Yamashita, N.; Giesy, J. P.; Zheng, J.; Fang,
Z.; Im, S. H.; Lam, P. K. S., Perfluorinated compounds in coastal
waters of Hong Kong, South China, and Korea, Environ. Sci. &
Technol., 2004, 38, 4056-4063.
􀁺 Tang, L.; Kebarle, P., Dependence of ion intensity in electrospray
mass spectrometry on the concentration of the analytes in the
electrosprayed solution, Anal. Chem., 1993, 65, 3654-3668.
􀁺 Taniyasu, S.; Kannan, K.; Horii, Y.; Hanari, N.;; Yamashita, N., A
Survey of perfluorooctane sulfonate and related perfluorinated
organic compounds in water, fish, birds, and humans from Japan,
Environ. Sci. & Technol., 2003, 37, 2634-2639.
􀁺 Taves, D. R., Evidence that there are two forms of fluoride in human
serum, Nature, 1968, 217, 1050-1051.
􀁺 Thomson, J. J., Ray of positive electricty and their application to
chemical analysis, Green and Co., 1998.
􀁺 Wong, S. F.; Meng, C. K.; Fenn, J. B., Multiple Charging in
Electrospray Ionization for Poly(ethylene glycols), J. Chem. Phys.,
1988, 92, 546-550.
􀁺 Yamashita, N.; Kannan, K.; Taniyasu, S.; Horii, Y.; Okazawa, T.;
Petrick, G. ; Gamo, T., Analysis of Perfluorinated Acids at Parts-
Per-Quadrillion Levels in Seawater Using Liquid Chromatography-
Tandem Mass Spectrometry, Environ. Sci. & Technol., 2004, 38,
5522-5528.
􀁺 Zeleny, J., Industry Application of Electrospray Technology, Phys.
Rev., 1917, 10, 1-6.