以超音波輔助分散式液液微萃取結合同步的衍生化方法快速檢測水樣中防曬乳成分之方法開發

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吳振文(Jen-wen Wu) 查詢紙本館藏

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論文名稱

以超音波輔助分散式液液微萃取結合同步的衍生化方法快速檢測水樣中防曬乳成分之方法開發
(Determination of UV-filters in water sample usingsimultaneous derivatization and ultra-sound assisted dispersive liquid–liquid microextractionfollowed by gas chromatography–mass spectrometry)

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摘要(中)

一個快速且有機溶劑用量少的方法檢測3種防曬乳成份ethylhexyl salicylate (EHS), 3,3,5-trimethylcyclohexyl salicylate (HMS), 2-hydroxy-
4-methoxybenzophenone (BP-3) 及兩種與BP-3有類似結構的羥基化二苯甲酮類2,4-Dihydroxybenzophenone (BP-1) 和 2,2’-Dihydroxy-4-methoxy
benzophenone (BP-8) 在水樣中的濃度。此方法利用超音波輔助分散式液液微萃取法 (Ultrasound-assisted dispersive liquid-liquid microextraction, UA-DLLME) 搭配同步 (In situ) 衍生化在一步中同時萃取及衍生化並利用氣相層析質譜儀來檢測。
利用兩個實驗設計方法：直交設計法 (Orthogonal array design, OAD) 與中央合成設計 (Central composite design, CCD) 來對萃取及衍生化的各項參數做一個探討，實驗所得最佳化條件為將萃取劑四氯乙烯 (tetrachloroethylene) 15 μL、與衍生化試劑 N,O-Bis(trimethylsilyl)
trifluroacetamide (BSTFA) 20 μL溶於分散劑丙酮 (acetone) 750 μL後快速打入10 mL含有0.5克氯化鈉的水樣當中，經過1分鐘的超音波震盪後以5000 rpm速率離心10分鐘後，利用60瓦225秒的微波功率及秒數來使衍生化更為完全。
　　在本研究的定量極限 (limits of quantitations, LOQs) 皆小於2 ng/L，而對其做精密度及準確度的測試，其相對標準偏差 (relative standard deviations, RSDs) 皆小於15 %，待測物的回收率介於62和92 %之間，利用標準添加法測得環境水樣中5種防曬乳成份的濃度在12.3到42.3 ng/L，而其中BP-3在環境水樣的所含濃度最高介於12.3到21.4 ng/L。
整體上來說，超音波輔助分散式液液微萃取法搭配同步衍生化是一個良好，且有效率的萃取水樣中防曬乳成份並可利用在環境的檢測上面，同時它是一個簡單、方便、快速、成本低且環保的一個實驗方法

摘要(英)

A rapid and solvent-minimized procedure for the determination of three UV filters: ethylhexyl salicylate (EHS), 3,3,5-trimethylcyclohexyl salicylate (HMS), 2-hydroxy-4-methoxybenzophenone (BP-3) and two related hydroxylated benzophenones (2,4-dihydroxy-benzophenone (BP-1) and 2,2’-dihydroxy-4-
methoxybenzophenone (BP-8)) in water samples is presented. The method involves one-step in-sample silylation coupled with ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) prior to their determination using gas chromatography-mass spectrometry (GC-MS).
The dual experimental design protocols (i.e., orthogonal array design (OAD) and central composite design (CCD)) to evaluate the effects of various derivatization and extraction parameters were investigated and the conditions optimized. The optimal derivatization and extraction conditions involved the rapid injection of a mixture of 750 μL of acetone (as a dispersant), 15 μL of tetrachloroethylene (as an extractant), and 20 μL of BSTFA (derivatizing agent) into a 10 mL of water sample containing 0.5 g of sodium chloride in a conical bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5000 rpm (10 min), the sedimented phase was then microwave irradiated at 60 W for 225 seconds to accelerate TMS-derivatization.
The limits of quantitations (LOQs) were less than 2 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 15% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 62 and 92%. Using a standard addition method, the preliminary results show that total concentrations of these five UV filters ranged from 12.3 to 42.3 ng/L, and BP-3 contributed the most to the total UV filters levels in water samples which ranged from 12.3 to 21.4 ng/L in this study.
Overall, one-step in-sample silylation coupled with UA-DLLME appears to be a good alternative extraction method for the determination of UV filters in environmental water samples, in that it is a simple, low cost, effective, and eco-friendly analytical method.

關鍵字(中)

★ 防曬乳
★ 超音波輔助分散式液液微萃取

關鍵字(英)

★ UV-filtersm
★ UA-DLLME

論文目次

中文摘要 ............................................................................................................. I
英文摘要 .......................................................................................................... III
謝誌 ................................................................................................................... V
目錄 .................................................................................................................. VI
圖目錄 ............................................................................................................... X
表目錄 ............................................................................................................. XII
第一章前言........................................................................................................ 1
1-1 研究緣起 ............................................................................................. 1
1-2 研究目標 ............................................................................................. 3
第二章文獻回顧 .............................................................................................. 4
2-1 新興汙染物 …………………………………………………………. 4
2-2 防曬乳成分 …………………………………………………………. 6
2-2-1 防曬乳成分介紹 ……………………………………………... 6
2-2-2 防曬乳成份的毒性 …………………………………………... 8
2-2-3 防曬乳成份的性質…………………………………………... 10
2-2-4 環境中防曬乳成分的來源 …………………………………. 13
2-2-5 國外相關文獻 …………………………….………………… 15
2-3 氣相層析質譜儀 ............................................................................... 19
2-4 衍生化介紹 ……………………………………………………… 21
2-4-1 衍生化技術的選擇及條件 ………………………………... 21
2-4-2 矽烷化反應 ………………………………………………... 22
2-5 超音波輔助萃取法 ………………………………………………. 25
2-6 分散式液液微萃取法 ………………………………………......... 26
2-6-1分散式液液微萃取法流程 ……………………..................... 26
2-6-2 影響分散式液液微萃取法效率之因素 ………………..... 27
2-6-3 超音波乳化微萃取法 .…………………….......................... 29
2-7 實驗設計 ……………………………………..………………..... 30
2-7-1 直交表設計………………………………………………..... 30
2-7-2 反應曲面法 ………………………………………………... 33
2-7-3中央合成設計 ……………………………………………..... 35
2-8 標準添加法 ……………………………………..……………..... 36
2-9 資料統計 ……………………………………..………………..... 38
第三章實驗步驟與樣品分析 ………………………..………………........ 40
3-1 實驗藥品與設備 ………………………………..……………..... 40
3-1-1 實驗藥品 ………………………………..………………... 40
3-1-2 儀器設備 ………………………………..………………... 42
3-2 實驗步驟 ……………………………………..………………..... 43
3-2-1標準品配置 ……………………………..………………....... 43
3-2-2 氣相層析質譜儀參數設定……………..………………....... 44
3-2-3 實驗流程………………………………..………………....... 45
3-2-4 實驗條件之探討 ……………………………..…………..... 46
3-3水樣採集 ………………………………………..……………….... 48
第四章結果與討論 …………………………..………………...................... 49
4-1 氣相層析質譜儀對矽烷基化待測物的測定……........................... 49
4-1-1 矽烷基化待測物的分析……..………………....................... 49
4-1-2 矽烷基化待測物質譜圖……..………………....................... 50
4-1-3 儀器偵測極限 ..……………..………………....................... 54
4-2 超音波輔助分散式液液微萃取條件最佳化 ……......................... 55
4-2-1 衍生化試劑種類……………..………………....................... 56
4-2-2分散劑及萃取劑的種類以及微波輔助衍生化 ..................... 58
4-2-3 分散劑、萃取劑及衍生化試劑體積 ………......................... 67
4-2-4 超音波震盪時間……………..………………....................... 72
4-2-5 pH值……………………………………..………………....... 74
4-2-6 鹽類添加量…………………………..………………........... 76
4-2-7超音波輔助分散式液液微萃取條件最佳化結果 …............ 78
4-3 線性關係及定量分析 ……………………..………………........... 80
4-3-1 線性關係及偵測極限 ……………………..………………. 80
4-3-2 線性方程式適用性 ……………………..…………............. 82
4-4 真實樣品之檢測 ……………………..………………................... 84
4-5 方法精密度及準確度………………..………………..................... 91
4-6 方法比較……………………..………………................................. 92
第五章結論　…………………………..……………….............................. 94
第六章文獻參考……………………..……………….............................. 95

參考文獻

? 周作潁、傅明仁，分散式液液微萃取技術搭配液相層析連結光二偶極陣列偵測器檢測環境中之苯脲型除草劑，民國 97 年 7 月。
? 葉怡成：二階反應曲面法之實驗設計，實驗設計法－製程與產品最佳化，6-1 - 6-7，民國 90 年。
? 曾新華、丁望賢：離子阱質譜儀，儀器總覽 - 化學分析儀器，民國 87 年。
? 黎正中、陳源樹譯：反應曲面方法與設計，實驗設計與分析 (Deisign and Analysis of Experiments 6/e)，第479 - 525 頁，民國95 年。
? Box, G. E. P., Draper, N. R.: Empirical Model-Building and Response Surfaces. Wiley 1987.
? Chen X, Bester K.: Determination of organic micro-pollutants such as personal care products, plasticizers and flame retardants in sludge, Anal Biochem. 2009 , 395, 1877-84.
? Chung, L. W.; Lin K. L.; Yang T. C.; Lee, M. R.: Orthogonal array optimization of microwave-assisted derivatization for determination of trace amphetamine and methamphetamine using negative chemical ionization gas chromatography–mass spectrometry, J. Chromatogr. A 2009, 1216, 4083–4089.
? Dı′az-Cruz, M. S.; Barcelo, D.: Chemical analysis and ecotoxicological effects of organic UV-absorbing compounds in aquatic, Trends Anal. Chem., 2009, 28, 708-715.
? Dı′az-Cruz, M. S.; Llorca M.; Barcelo, D.: Organic UV filters and their photodegradates, metabolites and disinfection by-products in the aquatic environment, Trends Anal. Chem., 2008, 27, 874-887.
? Giokas, D. L.; Sakkas, V. A.; Albanis, T. A.: Determination of residues of UV filters in natural waters by solid-phase extraction coupled to liquid chromatography–photodiode array detection and gas chromatography–mass spectrometry, J. Chromatogr. A 2004, 1026, 289–293.
? Giokas, D. L.; Sakkas, V. A.; Albanis, T. A.; Lampropoulou, D. A.: Determination of UV-filter residues in bathing waters by liquid chromatography UV-diode array and gas chromatography–mass spectrometry after micelle mediated extraction-solvent back extraction, J. Chromatogr. A 2005, 1077, 19–27.
? Giokas, D. L.; Salvador A.; Chisvert A.: UV filters; From sunscreens to human body and the environment, Trends Anal. Chem., 2006, 26, 360-374.
? Glassmeyer, S. T.; Furlong, E. T.; Kolpin D. W.; Cahill J. D.; Zaugg, S. D.; Werner, S. L.; Meyer, M.T.; Kryak, D.D.: Transport of chemical and microbial compounds from known wastewater discharges: potential for use as indicators of human fecal contamination, Environ. Sci. Technol. 2005 ,14 ,5157-5169.
? Jeon, H. K.; Chung, Y.; Ryu J. C.: Simultaneous determination of benzophenone-type UV filters in water and soil by gas chromatography–mass spectrometry, J. Chromatogr. A 2006, 1131, 192–202.
? Jeon, H. K.; Sarma, S. N.; Kim, Y. J.; Ryu, J. C.: Toxicokinetics and metabolisms of benzophenone-type UV filters in rats, Toxicology 2008, 248, 89–95.
? Kunz, P. Y.; Fent, K.: Estrogenic activity of ternary UV filter mixtures in fish (Pimephales promelas) — An analysis with nonlinear isobolograms, Toxicol. Appl. Pharmacol. 2009, 234, 77–88.
? Kunz, P. Y.; Fent, K.: Estrogenic activity of UV filter mixtures, Toxicol. Appl. Pharmacol. 2006, 217, 86–99.
? Kupper T.; Plagellat C.; Bra‥ ndli R.C.; de Alencastro L.F.; Grandjean D.; Tarradellas J.: Fate and removal of polycyclic musks, UV filters and biocides during wastewater treatment, Water Res. 2006, 40, 2603-2612.
? Li W. H.; Ma Y. M.; Guo C. S.; Hu W.; Liu K. M.; Wang Y. Q.; Zhu T.: Occurrence and behavior of four of the most used sunscreen UV filters in a wastewater reclamation plant, Water Res. 2007, 41, 3506-3512.
? Liu, H.; Liu, L.; Xiong, Y.; Yang, X.; Luan, T.: Simultaneous determination of UV filters and polycyclic musks in aqueous samples by solid-phase microextraction and gas chromatography–mass spectrometry, J. Chromatogr. A 2010, 1217, 6747–6753.
? Liu, Y. S.; Ying, G. G. Shareef, A.; Kookana, R. S.: Simultaneous determination of benzotriazoles and ultraviolet filters in ground water, effluent and biosolid samples using gas chromatography–tandem mass spectrometry, J. Chromatogr. A 2011, 1218, 5328– 5335.
? Luo, S.; Lin F. G., ; Wang X. W.; Liu H. T.; Ouyang, G. F.; Lan C. G.; Luan, T. G.: Determination of octylphenol and nonylphenol in aqueous sample using simultaneous derivatization and dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry, J. Chromatogr. A 2010, 1217, 6762–6768.
? Moeder, M.; Schrader, S.; Winkler, U,; Rodil, R,: At-line microextraction by packed sorbent-gas chromatography–mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples, J. Chromatogr. A 2010, 1217, 2925–2932.
? Moreta, C.; Tena, M. T.: Determination of UV filters in packaging by focused ultrasonic solid–liquid extraction and liquid chromatography, J. Chromatogr. A 2011, 1218, 3392–3399.
? Myers, R.H.; Montgomery, D.C.: Response Surface Methodology. Process and Product Optimization Using Designed Experiments. Wiley 2002.
? Negreira, N.; Rodríguez, I.; Rubí, E.; Cela R.: Optimization of pressurized liquid extraction and purification conditions for gas chromatography–mass spectrometry determination of UV filters in sludge, J. Chromatogr. A 2011, 1218, 211–217.
? Negreira, N.; Rodríguez, I.; Rubí, E.; Cela, R.: Determination of selected UV filters in indoor dust by matrix solid-phase dispersion and gas chromatography–tandem mass spectrometry, J. Chromatogr. A 2009, 1216, 5895–5902.
? Negreira, N.; Rodríguez, I.; Rubí, E.; Cela, R.: Optimization of pressurized liquid extraction and purification conditions for gas chromatography–mass spectrometry determination of UV filters in sludge, J. Chromatogr. A 2010, 1217, 211–217.
? Nguyen, K. T. N.; Scapolla C.; Carro M. D.; Magi, E.: Rapid and selective determination of UV filters in seawater by liquid chromatography tandem mass spectrometry combined with stir bar sorptive extraction, Talanta 2011, 85, 2375– 2384.
? Palit, M,; Mallard, G.: Dispersive derivatization liquid–liquid extraction of degradation products/precursors of mustards and V-agents from aqueous samples, J. Chromatogr. A 2011, 1218, 5393-5400.
? Robinson T.J., Myers R.H., and Montgomery D.C.: Analysis Considerations in Industrial Split-Plot Experiments When the Responses are Non-Normal, J. Qual. Technol. 2004, 36, 180-192.
? Poiger, T.; Buser, H. R.; Balmer, M. E.; Bergqvist, P. A.; M?uller, M. D.: Occurrence of UV filter compounds from sunscreens in surface waters: regional mass balance in two Swiss lakes, Chemosphere 2004, 55, 951–963.
? Rastogi, S. C.; Jensen, G. H.: Identification of UV filters in sunscreen products by highperformance liquid chromatography–diode-array detection, J. Chromatogr. A 1998, 828, 311–316.
? Rezaee, M.; Assadi, Y.; Hosseini, M. M.; Aghaee, E.; Ahmadi, F.; Berijani, S.: Determination of organic compounds in water using dispersive liquid–liquid microextraction, J. Chromatogr. A 2006, 1116, 1–9.
? Rodil, R,; Moeder, M.: Development of a method for the determination of UV filters in water samples using stir bar sorptive extraction and thermal desorption–gas chromatography–mass spectrometry, J. Chromatogr. A 2008, 1179, 81–88.
? Rodil, R,; Schrader, S.; Moeder, M.: Non-porous membrane-assisted liquid–liquid extraction of UV filter compounds from water samples, J. Chromatogr. A 2009, 1216, 4887–4894.
? Román, I. P.; Chisvert, A.; Canals, A.: Dispersive solid-phase extraction based on oleic acid-coated magnetic nanoparticles followed by gas chromatography–mass spectrometry for UV-filter, determination in water samples, J. Chromatogr. A 2011, 1218, 2467–2475.
? Said, T.; Dutot, M.; Martin, C.; Beaudeux, J. L.; Boucherd, C.; Enee, E.; Baudouin, C.; Warnet, J. M.; Rat, P.: Cytoprotective effect against UV-induced DNA damage and oxidative stress: Role of new biological UV filter, European Journal of Pharmaceu. Sci. 2007, 30, 203–210.
? Sánchez-Brunete, C.; Miguel, E.; Albero, B.; Tadeo, J. L.: Analysis of salicylate and benzophenone-type UV filters in soils and sediments by simultaneous extraction cleanup and gas chromatography–mass spectrometry, J. Chromatogr. A 2011, 1218, 4291– 4298.
? Schlumpf, M.; Kypke, K.; Wittassek, M.; Angerer, J.; Mascher, H.; Mascher, D.; Vökt, C.; Birchler, M.; Lichtensteiger, W.: Exposure patterns of UV filters, fragrances, parabens, phthalates, organochlor pesticides, PBDEs, and PCBs in human milk: Correlation of UV filters with use of cosmetics, Chemosphere 2010, 81, 1171–1183.
? Straub, J. O.: Concentrations of the UV filter ethylhexyl methoxycinnamate in the aquatic compartment: a comparison of modelled concentrations for Swiss surface waters with empirical monitoring data, Toxicol. Lett., 2002, 131, 29–37.
? Sun, L.; Lee, H. K.: Optimization of microwave-assisted extraction and supercritical fluid extraction of carbamate pesticides in soil by experimental design methodology, J. Chromatogr. A 2003, 1014, 165–177.
? Tarazona, I.; Chisvert, A.; León, Z.; Salvador, A.: Determination of hydroxylated benzophenone UV filters in sea water samples by dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry, J. Chromatogr. A 2010, 1217, 4771–4778.
? Vidal, L.; Chisvert, A.; Canals, A.; Salvador, A.: Ionic liquid-based single-drop microextraction followed by liquid chromatography-ultraviolet spectrophotometry detection to determine typical UV filters in surface water samples, Talanta 2010, 81, 549–555.
? Wick A.; Marincas O.; Moldovan, Z.; Ternes, T. A.: Sorption of biocides, triazine and phenylurea herbicides, and UV-filters onto secondary sludge, Water Res. 2011, 45, 3638-3652.
? Zenker, A.; Schmutzb, H.; Fent, K.: Simultaneous trace determination of nine organic UV-absorbing compounds (UV filters) in environmental samples, J. Chromatogr. A 2008, 1202, 64–74.

指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2012-6-27

推文