臺灣博碩士論文加值系統

近年來臭氧層遭受破壞，使得紫外線到達地面的強度逐漸增加，過量的紫外線會造成人體皮膚傷害，因此防曬產品使用量越來越多，為了發揮對市場監測及監督的功能，研究一為開發快速、簡單的分析方法，以氣相層析儀 ( GC-FID )同時進行六種常見化學性防曬劑之分析，有octyl salicylate ( OS )、oxybenzone ( BP3 )、octyl dimethyl PABA ( PO )、octyl methoxycinnamate ( OMC )、octocrylene ( OTC )、avobenzone ( AVO )，並以簡易的前處理方法進行市售防曬產品之分析及追蹤含量。本分析方法之同日間精密度為0.03－0.12%，異日間為0.03－0.28%，線性迴歸係數( R2 )均大於0.9999。各防曬劑化合物回收率介於98.25－101.91%，偵測極限為0.5 μg/mL，定量極限為1.0－1.5 μg/mL。本研究開發的分析方法，可大幅縮短分析時間，亦可供相關檢測單位及防曬劑製造廠來對其產品是否有超過限量的參考方法。
近期有機防曬劑已被歸類為環境中的新興汙染物，此類有害物質必須借助於各種分析技術來監控，於第二個研究中，開發了Vortex輔助乳化微萃取法搭配氣相層析質譜儀 ( GC-MS )，以一個快速且簡單的方法來檢測環境水樣中的有機防曬劑。Vortex輔助乳化微萃取技術需探討一些參數，如萃取溶劑種類與體積、pH影響、加鹽效應以及Vortex震盪時間，最後整合最佳化萃取條件為分析水樣調整pH 2.5、不需NaCl、加入萃取溶劑heptanol 50 μL，以Vortex震動5分鐘。在最佳化條件下之分析結果，線性濃度範圍50-1000 μg/L，線性迴歸係數( R2 )皆大於0.995，方法偵測極限為0.5－5.0 μg/L，定量極限為1.0－15 μg/L。同天的精密度在1.86－3.90%之間，連續六天精密度在1.22－7.69 %之間，濃縮倍率為186－304，此方法應用於游泳池水樣中六種分析物的相對回收率為90.32－111.27%，相對標準差皆小於8%，均有良好再現性。實驗證明只需少量且低毒性的萃取溶劑，並能短時間內完成萃取，此方法提供一個簡單、快速且對環境友善的萃取技術應用於環境中水樣。

In recent years the ozone layer is destroyed, so that the intensity of UV to reach the ground gradually increased, and excessive UV will cause harmful effects on human skin. A great number of sunscreen products with different UV filters are available in the commercial market. The purpose of the first study is to develop a quick and reliable analytical method to analyze six common UV-filters simultaneously. Six organic UV-filters including octyl salicylate ( OS )、oxybenzone ( BP3 )、octyl dimethyl PABA ( PO )、octyl methoxycinnamate ( OMC )、octocrylene ( OTC )、avobenzone ( AVO ) were analyzed by gas chromatography ( GC-FID ). And this method can analyze commercial sunscreen products after a simple pre-treatment. The precision of this method for intra-day was within 0.03%－0.12% . The precision for inter-day was within 0.03%－0.28% . The linear regression coefficient were
R2 > 0.9999. The recoveries were from 98.25 to 101.91% , limit of detection were less than 0.5 μg/mL and limit of quantitative were 1.0－1.5 μg/mL. The analytical method can substantially reduce the analytical time, and can be a reference tool for governments, relevant analysis institutes and sunscreen manufacturers.
In recent years, organic UV filters has been classified as emerging contaminants in the environment, so it has to monitor the hazardous substances by a variety of analytical techniques. In the second study, a quick and easy analytical method that vortex-assisted liquid–liquid microextraction ( VALLME ) coupled with gas chromatography-mass spectrometry ( GC-MS ) was developed for the analysis of organic UV filters in aqueous samples. VALLME studied variables were the type and volume of extraction solvent, pH effect, salt effect and vortex time. The optimized experimental conditions were 50 μL heptanol of the extraction solvent, vortex time of 5 mins, NaCl free and adjusted to pH 2.5 for aqueous samples. Under the optimized conditions, the results indicated that linear range of the method was 50-1000 μg/L with the R2 ≧0.995, the limits of detection ( LOD ) and the limits of quantification ( LOQ ) for the six target compounds were 0.5－5.0 μg/L and 1.0－15 μg/L . The precision for intraday was within 1.86－3.90%. The precision for interday was within 1.22－7.69 %, the enrichment factor between 186 and 304. The recoveries of spiked the swimming pool water samples were 90.32－111.27% with good repeatability and reproducibility ( RSD < 8% , n=3 ) for all the target compounds. These results indicated that the method provided a rapid, convenient and environmental friendly procedure for environmental samples.

摘要 I
ABSTRACT III
謝誌 V
目錄 VI
圖目錄 X
表目錄 XII
第一章 緒論 1
1-1 前言 1
1-2 研究目的 4
1-3 國內外之萃取水樣中防曬劑方法相關研究 6
第二章 文獻回顧 9
2-1新興汙染物 9
2-2防曬劑種類與作用 11
2-2-1 紫外線 ( Ultraviolet, UV )簡介 11
2-2-2 防曬劑簡介 15
2-2-3 防曬劑副作用 18
2-2-4 本實驗所研究之化學性防曬劑成分性質 21
2-3 氣相層析儀（GAS CHROMATOGRAPHY） 27
2-3-1 氣相層析火焰離子化偵測法 ( GC-FID ) 27
2-3-2 氣相層析質譜儀 ( GC-MS ) 28
2-3-2-1 電子撞擊游離法 30
2-3-2-2 四極柱質譜儀 31
2-4 各種微萃取法介紹 32
2-4-1 固相微萃取法 (Solid-phase microextraction) 32
2-4-2 液相微萃取法 ( Liquid-phase microextraction, LPME ) 34
2-4-3 分散式液液微萃取法 (Dispersive liquid–liquid microextraction, DLLME) 38
2-4-4 物理性輔助乳化微萃取法 41
第三章 實驗部分 43
3-1 實驗藥品與設備 43
3-1-1 藥品名稱及廠牌介紹 43
3-1-2 實驗儀器設備與裝置 45
3-2 實驗步驟 46
第一部分：以氣相層析儀分析六種化學防曬劑之研究 46
3-2-1 標準溶液配製 46
3-2-2 實驗儀器條件 46
3-2-3 氣相層析儀的參數設定 47
3-2-4 市售防曬產品溶液配製 48
第二部份：VORTEX輔助乳化微萃取結合氣相層析質譜儀測定水樣中六種化學性防曬劑之研究 49
3-2-5 標準溶液配製 49
3-2-6 實驗儀器條件 49
3-2-7 氣相層析質譜儀的參數設定 50
3-2-8 水樣萃取操作流程 51
3-2-9 真實水樣採集 52
第四章 結果與討論 53
第一部份 : 以氣相層析儀分析六種化學性防曬劑之研究 53
4-1 分析方法驗證 53
4-1-1 六種分析物之檢量線及偵測極限 53
4-1-2 分析方法之精密度 54
4-1-3 分析方法之準確度 56
4-1-4 市售防曬產品測試 58
第二部份：VORTEX輔助乳化微萃取結合氣相層析質譜儀測定水樣中六種化學性防曬劑之研究 62
4-2 VORTEX物理性輔助乳化微萃取法 62
4-2-1 萃取濃縮倍率及回收率的計算 62
4-2-2 萃取溶劑種類 63
4-2-3 萃取溶劑體積的影響 65
4-2-4 分析水樣pH值的影響 66
4-2-5 鹽類添加量的影響 68
4-2-6 Vortex震盪時間的影響 70
4-2-7 最佳化萃取條件 73
4-3 分析方法驗證及真實樣品測試 74
4-3-1 線性範圍、偵測極限、濃縮倍率及再現性 74
4-3-2 真實樣品檢測及回收率 76
第五章 結論 82
參考文獻 84

 
圖目錄
圖 1 1 防曬劑進入環境的途徑 3
圖 2 1 太陽光與紫外線能量關係 12
圖 2 2 物理性防曬劑作用機制 16
圖 2 3 化學性防曬劑分子內電子轉移之機制 17
圖 2 4 octyl salicylate化學結構圖 21
圖 2 5 oxybenzone 化學結構圖 22
圖 2 6 octyl dimethyl PABA化學結構圖 23
圖 2 7 octyl methoxycinnamate化學結構圖 24
圖 2 8 octocrylene化學結構圖 25
圖 2 9 avobenzone化學結構圖 26
圖 2 10 氣相層析儀架構 28
圖 2 11 質譜儀架構簡圖 29
圖 2 12 離子源撞擊圖 30
圖 2 13 四極柱質譜儀 31
圖 2 14 固相微萃取法(A) 頂空萃取 (B)直接萃取 33
圖 2 15 液相微萃取法裝置 34
圖 2 16 (A) 單滴液相微萃取法 (B) 頂空單滴液相微萃取法 35
圖 2 17 SDME 實際裝置 35
圖 2 18 HF-LPME裝置 36
圖 2 19 溶劑棒微萃取法裝置 37
圖 2 20 分散液液微萃取法 39
圖 3 1 水樣萃取操作流程 51
圖 4 1 防曬噴霧層析圖 58
圖 4 2 防曬凝膠層析圖 59
圖 4 3 防曬乳液層析圖 59
圖 4 4 萃取溶劑種類 64
圖 4 5 萃取溶劑體積的影響 65
圖 4 6 水樣pH值的影響 67
圖 4 7 鹽類添加量的影響 69
圖 4 8 超音波震動時間 71
圖 4 9 Vortex震盪時間 71
圖 4 10真實樣品之TIC圖 77
圖 4 11 Peak 1 質譜圖 78
圖 4 12 Peak 2質譜圖 78
圖 4 13 Peak 3質譜圖 79
圖 4 14 Peak 4質譜圖 79
圖 4 15 Peak 5質譜圖 80
圖 4 16 Peak 6質譜圖 80
表目錄
表1- 1 近十年水樣中防曬劑之萃取方法文獻整理 6
表1- 1 近十年水樣中防曬劑之萃取方法文獻整理(續) 7
表1- 1 近十年水樣中防曬劑之萃取方法文獻整理(續) 8
表2- 1紫外線分類及特性表 13
表2- 2紫外線氣象指標 ( UVI ) 14
表2- 3本實驗六種化學性防曬劑之防護波長與行政院衛福部所公告核准使用限量基準 20
表2- 4 octyl salicylate 命名及分子量 21
表2- 5 oxybenzone 命名及分子量 22
表2- 6 octyl dimethyl PABA 命名及分子量 23
表2- 7 octyl methoxycinnamate 命名及分子量 24
表2- 8 octocrylene 命名及分子量 25
表2- 9 avobenzone 命名及分子量 26
表2- 10分散液液微萃取法中最常使用的毒性有機萃取溶劑 40
表2- 11近五年來使用VALLME技術之研究 42
表3- 1 實驗藥品 43
表3- 2 分析物標準品 44
表3- 3 儀器設備名稱及廠牌型號 45
表3- 4 選擇離子偵測模式下定量離子 51
表4- 1 六種分析物之線性關係及偵測極限 53
表4- 2 滯留時間及面積比之精密度試驗結果 55
表4- 3 溶液安定性試驗結果 56
表4- 4 防曬噴霧、凝露、乳液三種劑型六種防曬劑之回收率 57
表4- 5 整合三種防曬產品之六種防曬劑滯留時間及層析峰面積 60
表4- 6 三種真實樣品之六種防曬劑含量 61
表4- 7 萃取溶劑性質介紹 63
表4- 8 比較Vortex和Ultrasonic萃取時間5分鐘之分析物訊號差異 72
表4- 9 最佳化的萃取條件 73
表4- 10 六種分析物之線性範圍、偵測極限、濃縮倍率及再現性 75
表4- 11 真實樣品回收率 81
表5- 1 本實驗以Vortex技術萃取防曬劑與文獻比較 83

1.行政院環境保護署: 認識紫外線 , 網址：http://taqm.epa.gov.tw/taqm/tw/b12081.aspx
2.Matsumura, Y.；Ananthaswamy, H.N.：Toxic effects of ultraviolet radiation on the skin. Toxicology and Applied Pharmacology 2004, 195:298– 308.
3.Narayanan, D.L.；Saladi, R. N.；Fox, J. L.：Review : Ultraviolet radiation and skin cancer. International Journal of Dermatology 2010, 49:978–986.
4.Balmer, M. E. ; Buser, H. R. ; Muller, M.D. ; Poiger, T.：Occurrence of some organic UV filters in wastewater, in surface waters, and in fish from Swiss lakes. Environ Sci Technol 2005, 39:953-962.
5.Schlumpf, M.；Schmid, P.；Durrer, S.；Conscience, M.；Maerkel, K.； Henseler, M.；Gruetter, M.； Herzog, I.；Reolon, S.；Ceccatelli, R.；Faass, O.；Stutz, E.；Jarry, H.； Wuttke, W.；Lichtensteiger, W.：Endocrine activity and developmental toxicity of cosmetic UV filters-an update. Toxicology 2004, 205:113-122.
6.Calafat, A. M. ; Wong, L. Y. ; Ye, X. ; Reidy, J. A. ; Needham, L.L.：Concentrations of the sunscreen agent benzophenone-3 in residents of the United States : national health and nutrition examination survey 2003-2004 . Environmental Health Perspectives 2008, 116:893-897
7.Giokas, D. L. ; Salvador, A. ; Chisvert, A.：UV filters: From sunscreens to human body and the environment. Trends Anal Chem 2007, 26:360-374.
8.Díaz-Cruz, D Barceló：Chemical analysis and ecotoxicological effects of organic UV-absorbing compounds in aquatic ecosystems. TrAC Trends in Analytical Chemistry 2009, 28: 708-717.
9.Daughton, C. G. ; Ternes, T. A.：Pharmaceuticals and personal care products in the environment: agents of subtle change? . Environ Health Perspect 1999, 107:907–938.
10.Rezaee, M. ; Assadi, Y. ; Milani Hosseini, M. R. ; Aghaee, E. ; Ahmadi, F. ; Berijani, S.：Determination of organic compounds in water using dispersive liquid-liquid microextraction. J.Chromatogr. A 2006, 1116:1-9.
11.Hadi, F. ; Parviz, N. ; Rassoul, D. ; Mohammad, R.：Development of dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry as a simple, rapid and highly sensitive method for determination of phthalate ester in water samples. J. Chromatogr. A 2007, 1172:105-112.
12.Wenting, Z. ; Lijun, H. ; Shuren, J. ; Zhigiang, Z. : Application of dispersive liquid-liquid microextraction for the analysis of organophosphorus pesticides in watermelon and cucumber. J. Chromatogr. A 2007, 1175:137-140.
13.Nagaraju, D. ; Huang, S.D.：Development of triazine herbicides in aqueous samples by dispersive liquid-liquid microextraction with gas chromatography-ion trap mass spectrometry. J. Chromatogr. A 2007, 1161:89-97.
14.Liang, P. ; Xu, J. ; Li, Q.：Application of dispersive liquid-liquid microextraction and High-performance liquid chromatography for the determination of three phthalate esters in water samples. Anal Chim Acta 2008, 609:53-58.
15.Sauvé, S.；Desrosiers, M.：A review of what is an emerging contaminant. Sauvé and Desrosiers Chemistry Central Journal 2014, 8.
16.CONTAMINANTS OF EMERGING CONCERN. WESTCAS Issue Paper Research and Technology.
17.United States Environmental Protection Agency : Contaminants of Emerging Concern. 網址: http://water.epa.gov/scitech/cec/.
18.Klaper, R.；Welch, L.C. : Emerging Contaminant Threats and the Great Lakes: Existing science, estimating relative risk and determining policies. Alliance for the Great Lakes 2011.
19.Raghav, M.；Eden, S.；Mitchell, K.；Witte, B. ：Contaminants of Emerging Concern in Water : Contaminants of Emerging Concern Raise Many Questions. Arroyo 2013.
20.Petrović, M.；Gonzalez, S.；Barceló, D. ：Analysis and removal of emerging contamination in wastewater and drinking water. Trends Anal Chem 2003:685-696.
21.Glassmeyer, S.T. ; Furlong, E.T.；Kopin, D.W. ; Cahill, J. D.；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, 39：5157-5169.
22.Glassmeyer, S.T.：The cycle of emerging contaminants. Water Resour IMPACT 2007, 9:5-7.
23.Richardson, S. D.：Water Analysis: Emerging Contaminants and Current Issues. Anal Chem 2009, 81: 4645–4677.
24.Lucas, R.；McMichael, T.；Smith, W. ；Armstrong, B.：Solar ultraviolet radiation: Global burden of disease from solar ultraviolet radiation. Environmental Burden of Disease Series 2006, 13.
25.World Health Organization：Ultraviolet radiation and the INTERSUN Programme.
網址 : http://www.who.int/uv/en/.
26.內爾阿德利著: 新世紀科學學習百科. 貓頭鷹出版部落格 1995.
27.交通部中央氣象局: 紫外線指數分級說明. 網址 : http://www.cwb.gov.tw/V7/observe/UVI/UVI.htm.
28.nutritionshopkeeper :紫外線圖譜, 網址 : http://nutritionshopkeeper.blogspot.tw/2010/09/uv.html. 2010.
29.Nohynek, G. J. ; Schaefer, H.：Benefit and risk of organic ultraviolet filters. Regulatory Toxicology and Pharmacology 2001, 33:285-299.
30.Wolf, R.；Tüzün, B.；Tüzün, Y. : Sunscreens. Dermatol Ther 2001, 14:208-214.
31.李仰川: 化妝品學原理 principles of cosmetics. 新文京開發出版有限公司 2003 , 第二版 ISBN 957-512-747-1
32.Lee, P. : Inorganic Sunscreens. Radiaton Protection Dosimetry 2000, 91:271-273.
33.Lansdown, A.B.G. ; Taylor, A.：Zinc and titanium oxides: promising UV-absorbers but what influence do they have on the intact skin ? . International Journal of Cosmetic Science 1997, 19: 167-172.
34.Wissing, S.A.；Müller, R.H. : The Development of An Improved Carrier System for
Sunscreen Formulations Based on Crystalline Lipid Nanoparticles. International Journal of Pharmaceutics, 2002, 242:373-375.
35.Nagtegaal, M.；Ternes, T.A.；Baumann, W.；Nagel, R.： Detection of UV-sunscreen agents in water and fish of the meerfelder maar the eifel,. Germany Z FurUmweltchem 1997, 9:79-86.
36.Kunz, P.Y.；Galicia, H.F.；Fent, K.： Comparison of in vivo estrogenic activity of UV filters in fish. Toxicology Science 2006b, 90:349-361.
37.Kunz, P.Y.；Fent, K.：Estrogenic activity of UV filter mixtures. Toxicology and Applied Pharmacology 2006, 217:86–99.
38.Weisbrod, C. J.；Kunz, P.Y.；Zenker, A.K.；Fent, K. : Effects of the UV filter benzophenone-2 on reproduction in fish. Toxicology and Applied Pharmacology 2007, 225:255–266.
39.Schlumpf, M.；Cotton, B.；Conscience, M.；Haller, V.；Steinmann, B.；Lichtensteiger, W.：In Vitro and in Vivo Estrogenicity of UV Screens. Environ Health Perspect 2001, 109:239-244.
40.Centers for Disease Control and Prevention : Oxybenzone (BP-3). 網址:http://search.cdc.gov/search?utf8=%E2%9C%93&;affiliate=cdc-main&;query=Benzophenone-3+.
41.行政院衛生福利部: 化粧品含有醫療或毒劇藥品基準(含藥化粧品基準)防曬劑. 2015/1/15彙整版.
42.Calafat, A.M.；Wong, L.Y.；Ye, X.；Reidy, J.A.；Needham, L.L.： Concentrations of the Sunscreen Agent Benzophenone-3 in Residents of the United States: National Health and Nutrition Examination Survey 2003–2004. Environmental Health Perspectives 2008, 116:893-897.
43.Negreira, N.；Rodriguez, I.；Ramil, M.；Rubi, E.；Cela, R.：Sensitive determination of salicylate and benzophenone type UV filters in water samples using solid-phase microextraction, derivatization and gas chromatography tandem mass spectrometry. Anal Chem Acta 2009, 638:36-44.
44.Agilent Technologies : 儀器概論-氣相層析儀
網址:http://www.aandb.com.cn/script/edfile/2008/10/20081016-222221-46115394.pdf.
45.Agilent Technologies - LCGC Editors : Introduction to Electron Impact Ionization for GC–MS. LCGC Chromatographyonlinecom Solutions for separation scientists 2012, 30.
46.Agilent Technologies : Gas Chromatography Mass Spectrometry Detector.
47.Dawson, P. H. : Quadrupole Mass Spectrometry and its Applications. Elsevier 1976:65-78. ISBN: 978-0-444-41345-1
48.Pawlisazyn, J. : Anal.Chem 1990, 62:2145-2148.
49.Jeannot, M. A.；Cantwell, F. F. : 1996.
50.Jeannot, M. A.；Cantwell, F. F. : Mass transfer characteristics of solvent exraction into a single drop at the tip of a syringe needle. Anal Chem 1997, 69:235-239.
51.Xu, Li.；Basheer, C. ；Lee, H. K.： Developments in single-drop microextraction (Review article). J CHROMATOGR A 2007, 1152:184-192.
52.Shen, G. ; Lee, H. K.：Hollow fiber-protected liquid-phase microextraction of trazine herbicides. Anal Chem 2002, 74:648-654.
53.Zhao, L. ; Lee, H. K.：Liquid-Phase Microextraction Combined with Hollow Fiber as a Sample Preparation Technique Prior to Gas Chromatography/Mass Spectrometry. Anal Chem 2002, 74:2486–2492.
54.Jiang, X. ; Lee, H. K.：Solvent Bar Microextraction. Analytical Chemistry 2004, 76:5591– 5596.
55. Regueiro, J.；Llompart, M.；Garcia-Jares, C.；Garcia-Monteagudo, J.C.；Cela, R.：
Ultrasound-assisted emulsification-microextraction of emergent contaminants and pesticides in environmental waters. J Chromatogr A 2008, 1190:27-38.
56.Robina, F. ; Feng-kai, L. ; Shaukat, S. F. ; Jian-jun, H.： Journal of Environmental Sciences 2003, 15:710-714.

57.Yiantzi, E.； Psillakis, E. ；Tyrovola, K. ；Kalogerakis, N. ： Vortex-assisted liquid-liquid microextraction of octylphenol, nonylphenol and bisphenol-A. Talanta 2010, 80:2057–2062.
58.Moradi, M. ；Yamini, Y.；Ebrahimpour, B. ：Emulsion-based liquid-phase microextraction: a review. Journal of the Iranian Chemical Society 2014, 11:1087-1101.
59.Harris, D. C. : Quantitative Chemical Analysis. ISBN 0716776944
60. Zhang, Y.；Lee, H. K.：Determination of ultraviolet filters in water samples by vortex-assisted dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry. J. Chromatogr. A 2012, 1249:25-31.
61.González-Hernández, P. ；Pino, V. ；Ayala, J.H. ；Afonso, A.M. ：A simplified vortex-assisted emulsification microextraction method for determining personal care products in environmental water samples by ultra-high-performance liquid chromatography. Anal. Methods 2015, 7: 1825-1833.
62. https://www.sigmaaldrich.com/taiwan.html
63. http://www.merck.tw/zh/index.html;jsessionid=86BCE41290E40505C759586BCFC6107F
64. 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. Journal of Chromatography A 2004, 1026: 289–293.
65. Petra, C. ; Ester, H.：Determination of UV filters and antimicrobial agents in environmental water samples. Anal Bioanal Chem 2007, 387: 1343–1350.
66. Migaku, K. ; Rie, I. ; Hidehiro, H. ; Naoyuki, E. ; Noriya, O. ; Koichi, S. ; Yasuo, S. ; Hiroyuki, N.：Simultaneous analysis of benzophenone sunscreen compounds in water
sample by stir bar sorptive extraction with in situ derivatization and thermal
desorption–gas chromatography–mass spectrometry. Journal of Chromatography A 2008, 1200: 260–263.
67. Ho, Y. C. ; Ding, W. H.：Solid-phase extraction coupled Simple on-line derivatization gas chromatography _tandem mass spectrometry for the determination of benzophenone-type UV filters in aqueous samples. J. Chin. Chem. Soc. 2012, 59: 107-113.
68. Ivan P., R. ; Alberto, C. ; Antonio, C.：Dispersive solid-phase extraction based on oleic acid-coated magnetic nanoparticles followed by gas chromatography–mass spectrometry for UV-filter determination in water samples. Journal of Chromatography A 2011, 1218: 2467–2475.
69. Basaglia, G ; Pietrogrande, M. C.：Optimization of a SPME/GC/MS method for the simultaneous determination of pharmaceuticals and personal care products in waters. Chromatographia 2012 75：361–370.
70. Zhang, H ; Lee, H. K.：Simultaneous determination of ultraviolet filters in aqueous
samples by plunger-in-needle solid-phase microextraction with graphene-based
sol–gel coating as sorbent coupled with gas chromatography–mass spectrometry.
Analytica Chimica Acta 2012 742：67– 73.
71. Wu, J. W. ; Chen, H. C. ; Ding, W. H.：Ultrasound-assisted dispersive liquid–liquid
microextraction plussimultaneous silylation for rapid determination of salicylate
and benzophenone-type ultraviolet filters in aqueous samples. Journal of
Chromatography A 2013 1302：20– 27.
72. Claudia P. da Silva ; Elissandro S. Emídio ; Mary R. R. de Marchi：UV filters in water samples: experimental design on the SPE optimization followed by GC-MS/MS Analysis. J. Braz. Chem. Soc. 2013 24：1433-141.
73. 丁怡然 ; 黄云 ; 赵婷婷; 蔡倩; 罗玉; 黄斌; 张榆霞; 潘学军：气相色谱⁃质谱法测定水体中５ 种典型有机紫外防晒剂. Chinese Journal of Chromatography. 2014 32：629-634.
74. Picot Groz, M. ; Martinez Bueno, M. J. ; Rosain, D. ; Fenet, H. ; Casellas, C. ; Pereira, C.
; Maria, V. ; Bebianno, M. J. ; Gomez, E.：Detection of emerging contaminants (UV filters, UV stabilizers and musks) in marine mussels from Portuguese coast by QuEChERS extraction and GC–MS/MS. Science of the Total Environment. 2014 493：162–169.
75. Benedé, J. L. ; Chisvert, A. ; Salvador, A. ; Sánchez-Quiles, D. ; Tovar-Sánchez, A.：
Determination of UV filters in both soluble and particulate fractions ofseawaters by dispersive liquid–liquid microextraction followed by gaschromatography–mass spectrometry. Analytica Chimica Acta. 2014 812：50– 58.
76. Claudia Pereira da Silva; Elissandro Soares Emídio; Mary Rosa Rodrigues de Marchi：
Method validation using weighted linear regression models for quantification of UV filters in water samples. Talanta. 2015 131：221–227.